HYDROGEN REPORT 2 HYDROGEN REPORT - Hydropole€¦ · Editorial 2 10 Years of HYDROPOLE 4 A historical technology for modern, sustainable and emission free hydrogen production 6 PEM

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HYDROGEN REPORT 2

HYDROGEN REPORTSWITZERLAND 2010/2011Major Achievements

Editorial

The economy in the industrialized world directly depends on the availability and con-sequently the price of resources. The most important resource is crude oil because itnot only delivers primary energy but also represents the most important energy sto-rage system for industrialized society. The worldwide average continuous power con-sumption is approximately 14•109 kW. The amount of energy stored worldwide isabout 2.5•1013 kWh which corresponds to 2.5•1012 kg oil or 2•1010 barrels. Furthermore,the economic benefit from fossil energy carriers during industrialization is 0.4US$/kWh. If we assume a 25% energy efficiency in conversion, the economic benefit isabout 150 US$/barrel. In October 2008, the price of oil reached the value of 150US$/barrel and this was the reason for the economic crises. Due to the reduceddemand for oil upon the economic crisis, the oil price dropped and is increasing againwith the growing economy. Therefore, we may anticipate the next economic crisis assoon as the oil price again reaches 150 US$/barrel, unless we succeed to decouple eco-nomic benefit from the availability of fossil fuels.

The future economy has to be based on closed cycles for materials and especiallyenergy resources. The last century was dominated by an economy of mining resour-ces, converting the resources and disposing the products in the environment. This isonly sustainable as long as nature and especially the living matter is able to compen-sate and close the cycles. However, we have reached in the 21st century a level ofmaterials and energy flows which approach worldwide limitations.

Switzerland has no natural materials resources and is therefore traditionally very sen-sitive to the use of resources. Switzerland is intensively working on the conversion ofrenewable energy and the hydrogen cycle: e.g. hydrogen production by electrolysis,dense hydrogen storage in solids and finally the combustion of hydrogen in fuel cells.Small and medium sized industry develops world leading technology and products fora sustainable future in Switzerland. Excellent research on the most important challen-ges of the future hydrogen society is performed in Swiss universities, universities ofapplied sciences and national research institutions.

The Swiss hydrogen association is a very appreciated platform for the exchange ofknowledge and a network for project partners, especially between industry and aca-demics. The achievements in research and industry presented in this report exhibitthe great level of accomplishment in Switzerland. The Swiss hydrogen report from2006 was devoted to the industry working in the field, the second report published in2008 was devoted to the research activities and the current report is an overview ofthe major achievements.

Dübendorf, 29. April 2010

Prof. Dr. Andreas ZüttelPresident Hydropole

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SWITZERLAND 2010/2011

HYDROGEN REPORT

Andreas Züttel

Editorial 2

10 Years of HYDROPOLE 4

A historical technology for modern, sustainable and emission free hydrogen production 6

PEM Electrolyzers generating Hydrogen enriched natural gas HENG from Renewable Energy Sources 10

Solar production of Hydrogen 12

Hydrogen Production: New Membranes for Alkaline Electrolysis 14

PECHouse: Creating hydrogen from sunlight and water 16

Achievements of today creates the future of tomorrow 18

Metal Hydride Storage for Seasonal Off-Grid Energy Storage of Renewable Energy Applications 22

The Lucerne University of Applied Sciences and Arts 24

Sfoe Hydrogen Research Program 25

Synthetic Sapphire 28

Hydrogen Technology in the “Self Sufficient and Sustainable Space Unit” 30

Hydrogen sponges at home, at work, at play 32

Hydrogen for Efficiency in Conversion 34

Applied Sciences on PEM - Fuel Cells in Biel 36

Hydrogen driven municipal vehicle (hy.muve): from the laboratory to the street 38

The hydrogen Canal Boat in Birmingham 40

Hydrides 42

Hydrogen Facts 44

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Table of Contents

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HYDROGEN REPORT 10 Years of Hydropole

The association was founded on 23. Nov. 2001 and islegally located in Monthey. The first president of Hy-dropole was Bernard Mudry, the former director ofDjeva. During the last 8 years, a solid network ofmembers in Switzerland was built up and the num-ber of members continues to grow every year and isalready greater than fifty. Approximately one thirdare from industry, one third from academic institu-tions and the remaining third are individual mem-bers. The board consists of 7 members: the president,the vice-president and 5 work group leaders.

Since 2006, Hydropole has been a member of the Eu-ropean Hydrogen Association (EHA). The associationis represented through its board members in severalpolitical and international research organizations inorder to actively connect members with key playersin the field of hydrogen worldwide.

Hydropole produces a hydrogen report every otheryear. The first report was devoted to the industry inSwitzerland and was published in 2006. This was fol-lowed by the second report which was about hydro-gen research in Switzerland published in 2008. Thecurrent report presents the major achievements inthe field of hydrogen science and technology inSwitzerland.

Hydropole organized the "Swiss village" at the WorldHydrogen Energy Conference (WHEC) in June 2006in Lyon, France. Seven Hydropole members repre-sented the activities in Switzerland. The exhibitionwas a big success and significantly increased the vis-ibility of our members. Hydropole was representedby A. Luzzi and F. Holdener at the WHEC in Brisbane,Australia in June 2008. The WHEC 2010 will takeplace in May 2010 in Essen, Germany. Hydropole will

The Swiss Hydrogen Association, HYDROPOLE,is the national network for hydrogen-relatedmatters in Switzerland. HYDROPOLE is a knowl-edge and information cluster focused on all as-pects of past, present and future use of hydro-gen. HYDROPOLE serves as a platform for re-search, development, industry and other public

or private organizations. HYDROPOLE fostersknowledge about hydrogen and its application inthe energy sector by providing information tothe general public, the educational sector, devel-oping industry as well as for policy needs. Theassociation maintains close links with other hy-drogen associations in Europe and worldwide.

Prof. Dr A. ZüttelPresident

Mr. E. BurkhalterVice-President

Mrs. C. GianolaSecretary

Prof. J.-F. AffolterAuditor

Dr. A. HegglinAuditor

Dr. D. SuterBoard member

Dr. U. VogtBoard member

Prof. M. HöckelBoard member

Mr. F. HoldenerBoard member

Dr. Ch. WieckertBord member

Hydropole Board

organize a “Swiss village” with 8 members from in-dustry, research and academia.

In February 2008 and 2009, Hydropole participatedin the Swiss Pavillion organized by the Swiss em-bassy in Japan (Dr. Felix Mösner) at the Hydrogenand Fuel Cell exhibition (FC Expo) in Tokyo, Japan. Theexhibition had more than 24000 visitors and was avery impressive event.

Hydropole, as a network, stimulates the collabora-tion between universities, institutions and industry.Numerous research and development projects havebeen created between the members. Examples in-clude the light weight SAM fuel cell car with a metalhydride storage system and the research and devel-opment project on new membranes for alkalineelectrolyzers.

In the first ten years of the existence of the hydrogenassociation Hydropole, the hydrogen community inSwitzerland has been brought closer together. Thepersonal contacts and the exchange of informationwithin the association are of great value for themembers. Furthermore, the association is wellknown outside Switzerland and makes a significantimpact in research and industry in Europe and Asia.

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Contact

Prof. Dr. Andreas Züttel (President)Mrs. Corinne GIANOLA (Secretary)Empa Materials Sciences & TechnologyDept. Environment, Energy and MobilitySect. 138 “Hydrogen & Energy”Überlandstrasse 129CH-8600 Dübendorf, Switzerland

e-mail: [email protected] Phone: +41 44 823 4692

URL: http://www.empa.ch/h2e

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Referencehttp://www.hydropole.ch

Fig.1: Hydropole Network

A historical technology for modern, sustainableand emission free hydrogen production

For the past few years, IHT (Industrie HauteTechnologie SA) has had activities in the field ofindustrial electrolyser plants, mainly installingretrofits in existing plants after 30 years of op-eration. As a result, IHT’s Board of Directors hasrealized that the company is ideally positionedto face the new challenges of the so-called “hy-drogen economy” using their highly sophisticat-ed high pressure electrolyser technology.

The alkaline high pressure technology, characterizedby high efficiency, reliability, flexibility and short re-sponse times, is ideal for integration into renewableenergy systems (RES), for pilot plants and for hydro-gen mass production farms. Therefore, in order toconsolidate its presence in these modern fields ofapplication, IHT has strengthened an already ambi-tious research and development program and fur-ther reinforces its international position of expertiseby attending the most prominent technology fairsin the world, such as the FC exhibitions in Tokyo andHannover. In addition to employing a strong and ex-perienced engineering team, IHT cooperates withtechnical schools and institutes such as HIT Lau-

sanne, Empa Dübendorf, the University of Fribourg,and the Technical University of Denmark, as well aswith industry partners in Switzerland and other Eu-ropean countries. The current R&D projects of IHTmainly concern the improvement of efficiency in al-kaline electrolysers. In addition, the European proj-ect WELTEMP in the 7th Framework Program ad-dresses high temperature electrolysis. In the SwissCTI project NMAE2, new types of separation mem-branes are being developed which aim to consider-ably increase electrolyser efficiency.

As part of the International Energy Agency (IEA) proj-ect, IHT also collaborates with the Aragon HydrogenFoundation (AHF) in Spain with the objective of an-alyzing and optimizing the integration of alkalinehigh pressure electrolysis into the “RES to H2” con-cept. As the first step, the ITHER project was realisedat “Walqa Technology Park”, in the AHF headquar-ters [Fig. 2]. A 10 Nm3 H2/h electrolyser and its asso-ciated plant are about to be commissioned . TheITHER project was awarded the first prize as a Tech-nology Demonstration by the International EnergyAgency in 2010. IHT also develops other products,such as small electrolyser units, and designs univer-sal testing equipment which are suitable for per-forming different tests on new cell types with thegoal of improving the electrolysis processes with re-spect to cost and performance.

Presently, IHT addresses requests for large hydrogenproduction plants for high demand applications byclients from the refinery, gas manufacture, agrarianand food industries [Fig 5]. The gases obtained by al-kaline electrolysis are free of CO, CO2, CH4 as well assulphurous and chlorinated components.

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HYDROGEN REPORT

Ernest Burkhalter

Fig.1:Main productionsite of IHT in Monthey(VS), Switzerland.

Fig.3: ITHER 10 Nm3

electrolyser

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History of the electrolyserIn the 1940s, the Swiss company Lonza SA, based inVisp, was faced with a growing need for hydrogen inits production activities in the field of chemistry. Atthat time, the management decided, for strategic rea-sons, to produce its own hydrogen and therefore man-dated one of their engineers, Ewald A. Zdansky, tostudy and develop a hydrogen generator that couldmeet the gas requirements for the production ofchemicals such as ammonia. The large availability andlow price of electrical power from hydropower sta-tions in Switzerland lead Zdansky to develop alkalineelectrolysis as the most effective process for hydrogengeneration. In Giovanola Frères SA (GFSA), located inMonthey [Fig. 4], he found the right partnership,equipment and large manufacturing experience forthe production and testing of the first prototype elec-trolysers. After a few years of development, the firstZdansky-system high pressure industrial electroly-sers, manufactured at GFSA, were commissioned byLonza [Fig. 3]. The design of this electrolyser waspatented by Lonza [Fig. 6, 7].

Originally, the main interest ofLonza was to produce hydrogenfor own chemical plant; however,when they realized the growinginterest from industry for the elec-trolyser, Lonza decided to sell therights resulting from the Zdansky

design to LURGI ("Metallurgische Gesellschaft"), alarge engineering company located in Butzbach, Ger-many. Continuing the cooperation with GFSA, LURGIbegan the commercialization of the high pressureelectrolysers. In the meanwhile, LURGI was also com-mitted to improving its design, particularly with re-spect to the electrodes [Fig. 8] and specific mechanical

constructions. The research and development wascarried out at GFSA and managed by Jürgen Bor-chardt, a LURGI engineer based in Monthey. He alsosupervised the fabrication of more than one hundredelectrolysers which were subsequently installedworldwide.

In 1996, LURGI discontinued electrolyser develop-ment and manufacturing and closed the electrol-yser section. The rights to the design, developments,and customer database were acquired by the man-ufacturing partner, GFSA. In 2001, GFSA faced finan-cial difficulties and soon after declared bankruptcy.Its daughter company, GTec SA, was subsequently

Table of technical data:

High Pressure Electrolysis Atmospheric ElectrolysisProduction capacity:Hydrogen: 110 to 760 Nm3/h H2 3 to 330 Nm3/h H2Oxygen: 55 to 380 Nm3/h O2 1.5 to 165 Nm3/h O2Gas purity levels:Hydrogen: 99.8 to 99.9 % vol. 99.8 to 99.9%Oxygen: 99.3 to 99.6 % vol. 99.5 to 99.8%Residual impurities:O2 in H2: 0.1 to 0.2 % vol.H2 in O2: 0.4 at 0.7 % vol.H2O: approximately 1 to 2 g/Nm3

KOH: less than 0.1 mg/Nm3

Consumption:Electrical energy: 4.3 to 4.6 kWh/Nm3 H2 3.90 to 4.22 kWh/m3 H2

(gas at 0°C, 1013 mbar, dry) (gas at 20°C, 1013 mbar, wet)Feedwater: 0.85 l/Nm3 H2 1 l/Nm3 H2Cooling water: 40 l/Nm3 H2 (∆t = 20°C) 60 l/Nm3 H2

Part-loads 25 to 100% of its nominal 25 to 100% of its nominal capacity capacity

Fig.4: Facilities of theGiovanola Frères SA (GFSA), located in Monthey, Switzerland

Fig.3: First prototype of an industrial Zdansky-electrolyser(1949).

created in 2002 by taking over GFSA’s activities andimplementing a new legal and financial structure.However, it also did not survive and later declaredbankruptcy as well. In 2003, the new IHT company In-dustrie Haute Technologie SA (IHT) was founded to re-sume the manufacture of Zdansky type electrolysers.IHT manufactures the Zdansky high pressure electrol-ysers in the original factory in Monthey [Fig. 1].

Today, IHT is a successful electrolyser manufacturingcompany with engineering, manufacturing and com-mercial activities. Having completed contracts in Swe-den, Switzerland and Argentinia, the company focus-es on the high demand of the world hydrogen market,where its unique large size electrolysers (up to 3.5MW) are ideal for mass production plant applications.

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References[1] Method for starting multicellular pressure

electrolysers", Ewald A. Zdansky, Monthey, Switzerland, U.S. Patent 2,683,116, 30. 11. 1949.

[2] "High-Pressure Electrolyze", E. A. Zdansky, (assigned to Lonza Elektrizitatswerke und chemische Fabriken Akt.-Ges.), Swiss Patent 330,814 (1958) August 15

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Contact

Ernest Burkhalter, CEOIHT, Monthey, Switzerland

Phone: +41 79 238 6474Fax: +41 24 471 9264e-mail: [email protected]

URL: http://www.iht.ch

Fig.7: Cross section of abipolar, atmospheric pressure electrolysis unitwith alkaline electrolyte(Brown Boveri) a) First anode with pre-electrode; b) Diaphragm; c) Pre-electrode of thecathode; d) Cathode for the firstcell compartment and an-ode for the second cellcompartment-bipolarmiddle electrode; e) Cell frame with insulation for the middleelectrode;f) Distribution pipe for electrolyte; g) Inlet pipefor electrolyte; h) Take-off system forelectrolyte and dissolvedgases; i) Overflow pipe and col-lecting vessel for elec-trolyte and H2 (an analo-gous system is used forO2); j) Electrolyte filter; k) Circulation pump; l) End plate

Fig.8: Cross section and exploded view of the cells of apressure electrolysis unit (Lurgi, Zdansky-Lonza pressureelectrolysis) a) Bipolar electrodes, dimple plate cell partiti-ton; b) Pre-electrodes in the form of nets on both sides ofthe asbestos diaphragm (c); d) Cell frame; e) Sealing ring,sealing the electrolyte against the surroundings and insu-lating the bipolar sections against each other; f) Electrolyteduct; g) Bore in the electrolyte duct for supplying the elec-trolyte solution to both sides of the electrolyte; h) ParallelH2 and O2 ducts; i) Bore in the gas duct; j) Electrolyte com-partment. Zero gap cell geometry. Perforated cathodes andanodes, in direct contact with the diaphragm and themembrane, respectively. The conical apertures with differ-ent diameters for O2 and H2, respectively, facilitate the de-tachment of the developing gas.

Fig.6: Patent of the Zdansky high pressure electrolyser.

Fig.5: High pressure electrolyser

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Hydrogen enriched natural gasIn the context of the “Sustainable Ameland”, Enecostarted a project involving the blending of hydrogenin the gas network. An innovative project that exam-ines the impact of blending hydrogen on various ma-terials. Using a blend of natural gas and hydrogen forheating and cooking saves energy.

The project, which was supervised by KIWA/Gastec, iscarried out at 14 households to gain experience withthe consequences of blending for heating and cook-ing purposes. Hydrogen is generated using electricityfrom renewable sources. The PEM type HOGEN® elec-trolyser is in successful operation since almost 2 years.

PEM Electrolyzers generating Hydrogen enrichednatural gas HENG from Renewable Energy Sources

Diamond Lite S.A., a Swiss based engineeringcompany with a European wide distribution net-work is providing on-site gas generation solutionsmainly for industrial applications. HOGEN® PEMsolid electrolyte hydrogen electrolyzers are usedsince a long time for many industrial applications,replacing hydrogen supply in cylinders. Proton Ex-change Membrane (PEM) diaphragm technology,was developed years ago by engineers in the con-

text of the NASA space program and which wasrefined for military applications. In the past years,Diamond Lite has also realized projects in connec-tion with renewable energy sources such as windand PV. The generated hydrogen is used for fuelcell vehicles or in other cases for stationary elec-tric power generation. This article reports about2 projects realized in 2008 and 2009.

Fig.1: HOGEN® hydrogen generator in container

Fig.2: Schematic diagramof the blending project

H. Vock

HENG BenefitsHENG enables the initial deployment of hydrogen inthe energy system without the need for expensive in-frastructure investments. This resolves the classic“chicken and egg” problem of hydrogen productionand the dedicated storage, transmission and otherequipment needed to use it directly as a fuel. The useof HENG enhances combustion and reducesCO2 emis-sion from natural gas. It also leads to lower emissionsof pollutants such as nitrogen oxide (NOx), carbonmonoxide (CO) and unburned methane and other hydrocarbons. HENG can also improve the fuel efficiency

of gas-fired combustion in boilers, engines and tur-bines, using existing natural gas delivery infrastructureand end-use equipment.

HENG increases the efficiency of natural gas conver-sion into useful energy. Adding even small amounts ofhydrogen leads to more complete combustion of thefuel, including CO, methane and other hydrocarbons inthe gas stream. This can improve engine efficiency andlower emissions of harmful pollutants.

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Street lights powered by fuel cellsIn order to reduce the dependency on heavy fuel oiland diesel for power generation, a hydrogen gener-ation and storage demonstration plant was in-stalled on the island of Porto Santo.

In a first stage, electricity from a renewable energysource (wind mill farm) is used to generate hydro-gen. The H2 is generated at 30 bar without compres-sor and stored in a tank. At night, hydrogen is fed to

fuel cells, to generate electricity for street lights onthis touristic island.

The installed plant is part of H2RES (Hydrogen fromRenewable Energy Source) model to be put in placefor the whole island. The H2RES concept is designedto balance on an hourly time basis the demands ofwater, electricity, heat and hydrogen supply fromavailable sources like wind, solar and others.

The operation of the complete system began in No-

Contact

H. VockDiamond Lite S.A.Rheineckerstr. 12PO Box 9 CH-9425 Thal, Switzerland

Phone: +41 71 880 02 00Fax: +41 71 880 02 01e-mail: [email protected]

www.diamondlite.com

References

www.duurzaamameland.nlwww.kiwa.nl

Rui Martins1, Goran Krajacic2, Luis Alves1, Neven Duic2, Toste Azevedo1 and Maria da Graça Carvalho1

1 Mechanical Engineering Department – Instituto Superior Técnico

2 Department of Energy, Power Engineering and Environment, Faculty of Mechanical Engineering and Naval Architecture, University of Zagreb, Croatia

Fig.3: General overview ofthe installation

Fig.4: HOGEN® 30 bar hydrogen generator

vember 2008. It has been proven, that the genera-tion of hydrogen from renewable sources and apply-ing a PEM electrolyser unit is a viable solution withinthe overall project goal.HOGEN® hydrogen generators can absorb excesspower from the wind turbine in a range from 0 to100% capacity without any problems.

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HYDROGEN REPORT Solar Production of Hydrogen

Fig.1: Thermochemicalpaths for H2 productionusing concentrated solarenergy.

The Solar Technology Laboratory at PSI and the Pro-fessorship of Renewable Energy Carriers at ETHZurich jointly perform research aimed at develop-ing solar thermochemical processes for the produc-tion of hydrogen, making use of concentrated solarradiation as the energy source of high-temperatureprocess heat [1,2]. State-of-the-art solar concen-trating facilities – solar furnace and high-flux solarsimulator – serve as unique experimental platformsfor the development of high-temperature thermo-chemical reactors.

The strategy for developing technically and eco-nomically viable solar chemical technologies forproducing hydrogen (H2) and syngas (mainly H2and CO) involves research on two paths (Fig. 1); (1) Long-term path via solar water-splitting ther-mochemical cycles, e.g. the ZnO/Zn cycle; (2) short/ medium-term path via solar decarboniza-tion of fossil fuels, e.g. cracking, reforming, andgasification processes. Benchmark is the waterelectrolysis using solar thermal electric power(central line).

Example: solar hydrogen via carbothermic pro-duction of zincThe so-called SOLZINC process for the solar carboth-ermic reduction of ZnO to Zn is shown schematicallyin Fig. 2. It is a near-term variant of a H2O-splittingcycle already realized at pilot scale and now ready forfurther up-scaling to industrial scale and commer-

cial application: ZnO is mixed with a carbon source,e.g. biochar, coal, or other carbonaceous materials.The mixture is heated with concentrated solar ener-gy to 1200 °C, at which the endothermic reactionZnO + C Zn + CO proceeds at a fast kinetic rate. On-ly 20% of the carbonaceous reductant consumed inthe conventional production of zinc is required forthe solar process. The solar-made zinc allows forstorage of solar energy. The exothermic hydrolysisreaction, Zn + H2O ZnO + H2, is decoupled fromthe availability of solar energy and can then be ac-complished on demand at the hydrogen consumersite. Alternatively, zinc may be used in Zn-air fuelcells/batteries for electricity generation. In eithercase, the chemical product is ZnO, which is recycledto the solar reactor. In the framework of an EU-fund-ed project with partners from France, Israel, andSweden, the SOLZINC reactor technology was suc-cessfully demonstrated in a 300 kW pilot plant atthe solar tower facility of the Weizmann Institute ofScience (Figs. 3 and 4), yielding 50 kg/h of 95%-purityZn with a solar-to-fuel energy conversion efficiency(ratio of the reaction enthalpy change to the solarenergy input) exceeding 30% [3].

Outlook and concluding remarksIn addition to further pursuing the SOLZINC process,PSI and ETH are jointly investigating the productionof Zn without any carbon by direct thermal dissoci-ation of ZnO [4]. Testing of a 100 kW solar pilot plantis planned for 2011. Another major solar chemicaldemonstration at 500 kW scale is the steam gasifi-

Christian Wieckert

Anton Meier

Aldo Steinfeld

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Fig.2: SOLZINC process forthe solar carbothermic reduction of ZnO and thecyclic processes for theon-demand production of solar hydrogen in a hydrolyser or solar electricity in a Zn-air fuelcell/battery.

cation of petroleum coke for the production of syn-gas (H2 and CO, which can be further processed toliquid fuels), scheduled for 2010 at the solar tower ofthe Plataforma Solar de Almería/Spain. The solar chemistry research program at PSI/ETH is

Contact:

Dr Christian Wieckert, Dr Anton Meier, and Prof. Dr Aldo Steinfeld, Paul Scherrer Institute, Solar Technology Laboratory, CH-5232 Villigen-PSI and ETH Zurich, Dept. Mechanical and Process Engineering, CH-8092 Zurich.

Phone: +41 56 310 4407e-mail: [email protected]

http://solar.web.psi.ch/, www.pre.ethz.ch/

References

[1] A. Steinfeld, A. Meier, “Solar Fuels and Materials”, Encyclopedia of Energy,Vol. 5 (2004), pp. 623-637.

[2] A. Steinfeld, “Solar Thermochemical Production of Hydrogen”, Solar Energy 78 (2005), pp. 603-615.

[3] C. Wieckert et al., ”A 300 kW Solar Chemical Pilot Plant for the Carbothermic Production of Zinc”, ASME J. Solar Energy Engineering 129 (2007), pp. 190-196.

[4] L. Schunk et al., “A Solar Receiver Reactor for the Thermal Dissociation of Zinc Oxide”, ASME J. Solar Energy Engineering 130 (2008), 021009.

[5] A. Z’Graggen, A. Steinfeld, “Hydrogen Production by Steam-Gasification of Carbonaceous Materials using Concentrated Solar Energy – V. Reactor modeling, optimization, and scale-up”, Int. J. Hydrogen Energy 33 (2008), pp. 5484-5492.

being funded primarily by the Swiss Federal Officeof Energy, Swiss National Science Foundation, SwissInnovation Promotion Agency, European Union, andprivate industry.

Fig.3: : The heliostat fieldof the solar tower facilityat the Weizmann Institute of Science (Israel)delivers concentrated solar radiation that is di-rected via a “beam-down”reflector to the 300 kWSOLZINC pilot plant installed on the ground.

Fig.4: The 300 kW SOLZ-INC solar reactor (left) isdesigned for a one batchper day operation. Zincvapor exits the reactor tothe off-gas system (right),where it rapidly condens-es to zinc dust.

ZnO + C →

Zn + CO

Reactants

Off-gas (CO)

C (coke, coal, biomass,..) Electricity

Zinc/Air Fuel CellZn + ½ O2 → ZnO

Solar Zn Reactor1200ºC

Beam Down Optical System

ZnO-Recycling

Zn

Hydrogen

Water-Splitting ReactorZn + H2O → ZnO + H2ZnO + C

→Zn + CO

Reactants

Off-gas (CO)

C (coke, coal, biomass,..) Electricity

Zinc/Air Fuel CellZn + ½ O2 → ZnO

Solar Zn Reactor1200ºC

Beam Down Optical System

ZnO-Recycling

Zn

Hydrogen

Water-Splitting ReactorZn + H2O → ZnO + H2

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HYDROGEN REPORT Hydrogen Production: New Membranes for Alkaline Electrolysis

Development of efficient hydrogen production isa high priority task for the growth of a sustain-able-energy society. The classical and environ-mentally clean production method of hydrogenis the electrolysis of water; however, it requireshigh energy costs. High pressure alkaline elec-trolysers are currently the most efficient and es-tablished type. One of the main components ofan electrolyser is the membrane between thecathode and the anode, separating hydrogen andoxygen gases; it strongly affects the energy con-sumption of the electrolyser and the gas purity.

The focus of the NMAE2 project is to study and devel-op new membranes integrated into high pressure al-kaline electrolysis cells to improve the electrolyser’sefficiency and replace membranes made from as-bestos, the use of which is prohibited by recent healthregulations. The new material needs to be imperme-able to O2 and H2, ion-conductive, stable in 25% KOHat 85oC (or higher) and 32 bars, flexible, robust and af-fordable. Chemical stability, porosity, ion conductivityand surface properties of new and traditionally usedmaterials were systematically investigated.

High gas purity (low gas penetration) is achieved bysmall pore size; the pores must be smaller than thehydrogen and oxygen bubbles. High ionic conductiv-ity in asbestos is mainly achieved through its excel-lent wettability, the effects related to the fibrousstructure and the specific multi-scale porosity. Theinterplay of surface processes most likely influencethe ion conductivity as well.

As one of the suitable materials, a 3-mol%-Y2O3-doped tetragonal-ZrO2 powder was chosen due toits high chemical stability in hot KOH electrolyte. Thefirst diaphragms were tested using an electrolyticcell lab setup with a current density of 200 mA/cm2

at ambient conditions and revealed positive results.These data combined with impedance, X-ray photo-electric, Raman spectroscopy, and electron micro-scopic measurements allow the evaluation of othercandidate materials for new membranes and theirfurther development.

Further promising materials and production meth-ods are currently undergoing the patenting proce-dure.Valentina

Zakaznova-Herzog

Fig.1: High pressure alkaline electrolyser (left) and theschematic view of the electrolysis unit: bipolar electrode(a), pre-electrode(b), diaphragm (c), pre-electrode(d), bipo-lar electrode(e). All elements include hydrogen and oxygenducts above and electrolyte duct below.

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Contact:

Dr Valentina Zakaznova-Herzog, Ernest Burkhalter, Dr Ulrich Vogt, Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Hydrogen & Energy, CH-8600 Dübendorf


www.empa.ch/h2e

References

Gorbar et al., "Porosity graded ZrO2 diaphragms for alkalineelectrolysis" 4th Int. Symposium Hydrogen & Energy, Switzer-land, 2010Wiedenmann D. et al., Impact of multi-scale pore structureon ion conductivity of asbestos gas separation diaphragmsfor alkaline water electrolysis". 4th Int. Symposium Hydrogen& Energy, Switzerland, 2010

Fig.2: Electrolysis test cells: (a) cell with two reference electrodes; (b) Cell type "Electra", made from hot alkali resistant polymer, integrated in the testbench, provides testing of the membrane resistance, and corresponded oxygen and hydrogen gasses flow and purity; (c) high pressure and high tempera-ture cell-stack, integrated in the test bench, provides testing of the membrane resistance, and corresponded oxygen and hydrogen gasses flow and purityup to 100oC and 35 bars.

Fig.3: Scanning electron microscopy shows a heteroge-neous asbestos diaphragm structure, composed of 3 phases: (1) solid silicate phase, (2) macro pores in m-scale,and (3) a mixture of asbestos nano fibres and pores in µm-scale (nano porous material). (Wiedenmann et al., 2010)

Fig.4: ESEM images of zirconium oxide basedmembranes obtained byaddition of gradedamount of carbon powder 10, and 30 vol.%,pressed at 20 kN and subsequently sintered at1200°C / 1 hour (top); ofzircon oxide based membrane obtained byaddition of gradedamount of carbon fibers10, and 30 vol.%, pressedat 50 kN and subsequent-ly sintered at 1200°C / 1 hour (below). (Gorbar et al., 2010)Fig.5: Experimental electrolysis test set up operated by M.

Gorbar.

a) b) c)

Zakaznova-Herzog V., Stojadinovic J.,Gorbar M., WiedenmannD.,Grobéty B.,Vogt,U., Züttel A., "Hydrogen production by alka-line electrolysis: is there a way to increase its efficiency by im-proving a separating membrane?" International Journal of Hy-drogen Energy (to be submitted)Zakaznova-Herzog V. et al.,, "Hydrogen production by alkalineelectrolysis: surface and electrochemical investigations of ma-terials for diaphragms" 4th Int. Symposium Hydrogen & Ener-gy, Switzerland, 2010

16 2


HYDROGEN REPORT PECHouse: Creating hydrogen from sunlight and water

Using abundant and renewable natural resources toproduce hydrogen in a carbon-neutral, sustainablemanner is a fundamental requirement for a futurehydrogen economy. This goal can be accomplishedusing sunlight to split water into hydrogen and oxy-gen in a photoelectrochemical (PEC) device. For thepast two years, PECHouse, a photoelectrochemicalcenter of excellence funded largely by the Swiss Fed-eral Office of Energy and led by Prof. Michael Grätzelat the Ecole Polytechnique Fédérale de Lausanne(EPFL) has been leading efforts for PEC hydrogen pro-duction in Switzerland. The approach of PECHouse isto use semiconducting materials made from abun-dant and inexpensive elements which absorb solarlight and catalyze water decomposition. Decades ofprevious studies have shown that it is unlikely thatresearch will identify one material which satisfies allof the necessary requirements of stability and lightabsorption. Accordingly PECHouse is pursuingmethods of using combinations of materials to splitwater into hydrogen and oxygen using sunlight in acost effective manner. The prototypical example ofthis is a tandem cell approach (Figure 1) where asemitransparent photoanode made of iron oxide(hematite, an inexpensive, stable and non-toxicsemiconducting mineral) absorbs light and cat-alyzes the oxygen evolution while the light not ab-sorbed by the iron oxide is transmitted and absorbed

by another photoelectrochemical system, for exam-ple a dye-sensitized solar cell, which provides addi-tional energy for the hydrogen evolution. In 2006the laboratories of Prof. Grätzel reported benchmarkperformance with iron oxide by properly nano-struc-turing and doping the material using an inexpensivedeposition method: particle assisted metal-organicchemical vapor deposition at atmospheric pressure(APCVD). [1] This breakthrough demonstrated theability of iron oxide to convert up to 3.3 % of the sun’senergy into hydrogen. Since this account, PECHousehas increased performance and the knowledge ofthe iron oxide APCVD system. A recent report in theJournal of Physical Chemistry details the advantagesand limitations of the APCVD iron oxide and identi-fies the pathways for further improvement (see Fig-ure 2). [2] PECHouse has ambitious goals for improv-ing these iron oxide photoanodes, with objectiveperformances of 7.5 % solar-to-hydrogen conversionby the end of 2011. To help accomplish this, PECHousehas gathered a team of European experts in a collab-orative consortium called NanoPEC. With a budgetof over 3.6 M€ over three years, NanoPEC consists of8 academic or industrial research groups which fo-cus on different aspects of applying nanotechnologyto materials for photoelectrochemical hydrogenproduction. An important demonstration of one ofthe concepts pursued by NanoPEC, the host ab-

Fig.1: Tandem cell approach for solar photo-electrochemical hydrogenproduction.

Michael Grätzel

17


HYDROGEN REPORT

2

sorber/guest scaffold approach, was recently pub-lished by PECHouse members in the journal Chem-istry of Materials. [3] Here, overcoming the poorsemiconducting properties and light absorption ofiron oxide is accomplished by depositing an ultrathin absorber layer on a rough scaffold material. Inorder to maximize the light absorption by the thinlayer of absorber the scaffold must be highly nanos-tructured. By using a tungsten oxide scaffold coatedwith nanoparticles of iron oxide PECHouse was ableto show a 20% increase in single light wavelengthefficiency with green light (565 nm). In addition tothe research on new nanostructures, NanoPEC andPECHouse are researching new in expensive materi-als and catalysts that will further enhance the watersplitting reaction for the goal of producing a devicethat can produce hydrogen from sunlight at a costof less than 4€/kg by 2012.

References

[1] Kay, A., Cesar, I., Gratzel, M.: New benchmark for water photooxidation by nanostructured alpha-Fe2O3 films. J. Am. Chem. Soc. 128, 15714 (2006).

[2] Cesar, I., Sivula, K., Kay, A., Zboril, R., Graetzel, M.: Influence of Feature Size, Film Thickness, and Silicon Doping on the Performance of Nanostructured Hematite Photoanodes for Solar Water Splitting. Journal of Physical Chemistry C 113, 772 (2009).

[3] Sivula, K., Le Formal, F., Gratzel, M.: WO3-Fe2O3Photoanodes for Water Splitting: A Host Scaffold, GuestAbsorber Approach. Chem. Mater. 21, 2862 (2009).

Fig.2: Scanning electronmicrograph of the nanos-tructured iron oxide usedfor watersplitting. The effect of the synthesistemperature on the feature size here is apparent. a) Cross-sectionat 470°C b) 450 °C and c)490 °C top down.

Contact

Prof. Michael GrätzelSwiss Federal Institute of Technology Lausanne Institute of Chemical Sciences and EngineeringLaboratory of Photonics and InterfacesEPFL-SB-ISIC-LPI, CH G1 526, Station 6CH-1015 Lausanne, Switzerland

Phone: +41 21 693 3112 Fax: +41 21 693 6100e-mail: [email protected]

http://isic.epfl.ch/lpi

18 2


HYDROGEN REPORT Achievements of today creates the future of tomorrow

NOVA SWISS® is active since more than 25 yearsin the creation of the future – with high pressurevalves and products for the hydrogen industry.Continuous developments result in diversifieduse.

We all know that hydrogen is something special.Being the most abundant of all elements whichexist in the universe does not automaticallymean that the lightest gas is an easy task to han-dle. Until today, handling and storage of hydro-gen requires special technologies. Thus, to findthe best solution is a continuous task that ischallenging research and development.

With the NOVA SWISS® trademark, Nova WerkeAG develops and produces high-quality, stan-dardized as well as customized high pressurecomponents and systems for hydrogen in pres-sure ranges from 500 – 4000 bar as well as otherfluid and gases in pressure ranges from 500 –10000 bar.

For example, Nova Werke AG provides reliable tech-nology for difficult conditions in hydrogen stationsbecause it has excellent knowledge of materials,clean processing and last, but not least, extensive ex-perience with the medium for more than 25 years.The latest technology of finite elements analysis aswell as rational planning with CAD support for visu-alisation in early project phases guarantees well-conceived solutions.

In the meantime it is a proven and standardizedtechnology for Nova Werke AG. For instance, in hy-drogen high pressure valves no O-rings are requiredanymore. The valves are leak-tight with metal tometal seals. NOVA SWISS® regulation valves canchange the flow characteristics according to differ-ent pressures.

Another field of substantial research and develop-ment has been the diaphragm compressors for hy-drogen. NOVA SWISS® diaphragm compressors forhydrogen are working for pressure ranges of up to1000 bar as well as 3000 bar. They are electricallypowered. The inlet pressure should be minimum 20bar. Depending on this inlet pressure, the capacityand discharge pressure can be calculated according-ly. NOVA SWISS® diaphragm compressors also havecapacities of up to 4 Nm3/hour, which is the rightsize for R&D centres, universities as well as laborato-ries.

Matthias Duvenbeck

Fig.1: Installation of 1000 bar pneumaticallydriven valves in hydrogenstations

Fig.2: Hydrogen station

Fig.3: Pneumatic driven valves

19


HYDROGEN REPORT

2

The advantage of the compact NOVA SWISS® di-aphragm compressor is the cleanliness of the com-pressed hydrogen. There is no contact between gasand oil. In the gas chamber there are no non-metal-lic-elements, which means that operating with ul-tra-pure hydrogen is possible. Dynamic sealing prob-lems are not possible because the piston is driven bycross head without additional gasket.

Nova Werke AG is operating from its modern state-of-the-art facilities with latest in-house materiallabs in Effretikon near Zürich. Well-known compa-nies active in the hydrogen industry, e.g. R&D Cen-tres, universities, producers of hydrogen and otherindustries have trusted Nova Werke for many yearsand rely on a careful selection of materials and pre-cise manufacturing.

NOVA SWISS® achievements of today do not meanthat the end of development is reached. As a matterof fact, the next generation of NOVA SWISS® prod-ucts for the hydrogen future is already in thepipeline.

Contact:

Matthias DuvenbeckNova Werke AGVogelsangstr. 24CH-8307 Effretikon

Phone: +41 52 354 16 04 Fax: +41 52 354 16 88e-mail: [email protected]

www.novaswiss.com

Fig.4: A compact diaphragm compressor,max. 3000 bar


HYDROGEN REPORT

Empa has many facets – but one common goal: to turn research into marketable innovations.A sustainable energy supply for the post-oil era is one focus of our R&D activites,for instance in the areas of hydrogen storage, fuel cells, photovoltaics and biogenic fuels.

www.empa.ch

Use-inspired research

Innovative developments

Knowledge & technology transfer

Services & expertises

Que

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21


HYDROGEN REPORT

2

Packed with Energy. Hydrogen solutions from LindeGas/PanGas.

Production

3 Linde builds and operates Hydrogen production plants from laboratory scale up to 100’000 Nm3/h3 In Ingolstadt and Leuna, Linde operates Germany‘s only large industrial Hydrogen liquefaction plants

Distribution

3 PanGas offers Hydrogen in cylinders and cylinder-batteries up to 300 bar filling pressure3 With GH2-trailers and LH2-vehicles PanGas offers concepts to ensure the economic distribution of Hydrogen

Applications

3 PanGas offers Hydrozon®, Hycontrol® and Hydroflex™-heat treatment processes for metals3 PanGas engineers create tailor-made supply systems for pure Hydrogen and Hydrogen-mixtures3 PanGas offers as well Linde‘s unique Hydrogen infrastructure systems for automotive applications

PanGas – Ideas become solutions.

PanGas AG

Hauptsitz, Industriepark 10, CH-6252 Dagmersellen

Telefon 0844 800 300, Fax 0844 800 301, www.pangas.ch

22 2


HYDROGEN REPORT Metal Hydride Storage for Seasonal Off-Grid Energy Storage of Renewable Energy Applications

Off-grid applications are far more complex than tra-ditional grid-connected energy systems. They re-quire large energy storage capacity while at thesame time having highly fluctuating energy input.While batteries can in principle offer the serviceneeded, storing large amounts of energy results inhigh volume, weight and capital cost. While forshort time intervals these parameters are less crit-ical, on a seasonal level they are cruicial. Hydrogenis capable of performing this task. Considering thecost per energy, weight and volume stored, the tech-nology is clearly beneficial and self discharge is notan issue.

For seasonal applications, pressurized storage is of-ten ruled out by space constrains (without com-pression) or prohibitive cost (with compression).Metal hydrides store hydrogen in solids. A metalhydride acts, bluntly speaking, as a "hydrogensponge"; but, in contrast to water, hydrogen is a gasand is therefore compressible. The gas is absorbedand densely packed within the material by theaffinity of the alloy towards hydrogen: almost likean "internal compression". As a result, hydrogen isabsorbed and stored at low pressure and at highvolumetric storage density while capacity simplydepends on the amount of material used. As a con-sequence of the condensation of hydrogen withinthe material, the gas undergoes a transition froma disordered to an ordered state (entropy change).

The result is an exothermic (charging) or endother-mic (discharging) reaction. Thermal flow andcharge/discharge rate are inherently coupled inmetal hydrides; to make it fast, tone must optimizethermal flow. While in fast applications this re-quires a great deal of engineering and a liquid heatexchange medium, for seasonal storage (where therate is low compared to total capacity) this param-eter is met by the ambient air which removes orsupplies heat at the necessary rates.

The hydrogen pressure in the hydride depends onthe material used, temperature and charging stateof the reservoir and is descirbed by the pressure-concentration-isotherm which is unique to eachmaterial. Applying a higher pressure than theplateau pressure leads to charging while loweringthe pressure below the plateau will lead to dis-charging of the container. The specifications of theindividual application (minimum charging pres-sure, minimum discharging pressure, Tmax, Tmin)define the potential choice of alloy materials.Empa has developed storage units based on a mul-titude of alloys for a variety application fields andsizes. Currently, units are in operation for boatpropulsion and units are built for seasonal energystorage: two distinctly different fields with uniquerequirements. Some of the units have been testedfor over 1000 cycles without any loss of capacity.

Michael Bielmann

Fig.1: : model off-grid system without hydrogen(3.6 kWp PV and 50 kWhbattery) in Zurich. Theload varies between 2kWh and 6 kWh per day(excl. cooking). Almost55% of the energy remains unused. This energy is available to produce hydrogen for later use.

23


HYDROGEN REPORT

2

Metal hydrides offer unique opportunities for stor-ing large amounts of energy in a small package. Al-though their characteristics require proper engi-neering for the specific application, this knowledgeis available. They outclass batteries in storageweight, volume and cost, by a large margin. Whileproduction of hydrogen and its reconversion toelectricity or heat have an efficiency penalty andare still costly, there is a large unrealized cost-re-duction potential in the technology. In most off-grid systems, the supply side must be oversized tomeet production capacity needs in winter or badweather phases. Assuming a constant load yearround, almost 80% of the produced energy is wast-ed due to storage constraints. Producing hydrogenwith the associated efficiency criteria is thereforefar less critical. For long time scales, batteries arejust not capable of delivering the service required:the choice is "use it or waste it".

Contact

Dr Michael BielmannEmpa, Swiss Federal Laboratories for Materials Science andTechnologyHydrogen and EnergyÜberlandstrasse 129CH-8600 Dübendorf


www.empa.ch/h2e

www.hydrogen.bham.ac.uk/protium.shtml

Fig.2: Essential storageparameters: energy density per volume, energy density per massand amount of energystored per unit cost forbatteries and hydrogenstorage media. Basis: 150Wh/kg, 400 Wh/L, 500CHF/kWh (Lithium Ion)and 25 Wh/kg, 60 Wh/L,150 CHF/kWh (Lead Acid).The cost for hydrogenstorage reflects prototypeunits built at Empa andtherefore offers high costreduction potential.

Table 1 : Specifications of the metal hydride storage unitfor seasonal energy storage

Fig.3:metal hydride storage unit for seasonalenergy storage

pmin (T=40°C) (charge) 10barpmin (T=0°C) (discharge) 1.5barStored amount of hydrogen >2.7kgEnergy equivalent 106kWhSystem volume 240LNumber of modules 6Container material Al 7000-alloyTotal System weight 300kg

2

24 2


HYDROGEN REPORT

Contact

Dipl.-Ing. Ulrike TrachteLucerne University of Applied Sciences and ArtsCC Thermal Energy Systems & Process EngineeringTechnikumstrasse 21CH-6148 Horw, Switzerland

Phone: +41 41 349 3311 Fax : +41 41 349 3960e-mail: [email protected]

www.hslu.ch/technik-architektur

The Lucerne University of Applied Sciences and Arts

is a regional, public-funded university in CentralSwitzerland. More than 5500 students are enrolledin Bachelor and Master programmes. It comprisesfive campuses, all of them centrally located in oraround the city of Lucerne. The campus of LucerneSchool of Engineering and Architecture offers a widearray of courses in various technical fields. The activ-ities of the Lucerne School of Engineering and Archi-tecture are focused on applied research and devel-opment and on close cooperation with local indus-try, business and institutions.In the field of energy the main subjects are thermalenergy systems, process optimisation, energy stor-ages including supercapacitors and system integra-tion.

Hydrogen & Fuel Cell activitiesIn the field of hydrogen and fuel cells (FC) theLucerne School of Engineering and Architecture isspecialised in system integration and testing of FC’sin concrete applications. One project is the ‘PEM Fu-el-Cell Back-Up System’, which is realised with twoindustrial partners and financial support of theSwiss federal office of energy (SFOE). In this project, the lead-acid batteries of an uninter-ruptible power supply system (UPS) were replacedby a 10 kW PEM FC System. The delayed start-up be-haviour of the FC is bridged with supercapacitortechnology. The system is connected to an existingworking base station of a telecommunication instal-lation since January 2006.Hydrogen is supplied by two 50 l pressure tankswhich provide a stand-alone operation for about 6hours under antenna load.

The field test is performed under real conditionswith monthly grid failure simulations. Excellent re-sults of the approximately 350 start-up’s to dateconfirm the functionality, reliability and perform-ance of the system.

Achievements of the FC UPSDuring the project period over more than three yearsthe market changed. An increasing number of FC

producers and UPS suppliers became aware that theapplication of FC’s as a back-up system respond tocritical market demands. They developed ready-to-market products which are suited to achieve earlycommercialisation success. Hence for the FC UPS ap-plication it is no longer the question of functionalitybut of a successful market entry.This early market is now supported by the FC and Hy-drogen Joint Undertaking (FCH JU) Program. In thisprogram a call has been announced to demonstratethe application readiness of these back-up systemsand to contribute to a widespread acceptance of thisnew technology. The Lucerne School of Engineering and Architecturewill continue its involvement in this segment. It willstrengthen the activities in concrete FC applications,testing and demonstration of FC deployment.

Ulrike Trachte

Fig.1: Energy related research subjects

Fig.2: Hydrogen storage for telecommunications

FC System integra- Integration of tion & Field test Supercapacitors

Sfoe Hydrogen Research Program

As an energy source, hydrogen can make a signifi-cant contribution towards the achievement of theambitious objectives of European and Swiss policiesfor the coming decades relating to energy supply se-curity, reduction of CO2 emissions and industrial in-novation. Within the Swiss long-term energy per-spectives hydrogen continues to own a major poten-tial as energy carrier that is absolutely needed whenfacing storage problems in a future energy supplybased on renewable energy sources.

In Switzerland, hydrogen has been the subject of en-ergy research for several decades. Swiss Institutionsare among the world leaders in terms of expertise inresearch and development, both at the Federal Insti-tutes of Technology, universities and colleges oftechnology, as well as in small and medium-sizedcompanies. The research currently being carried outis to a large extent integrated into international proj-ects. The national hydrogen research programme,which is part of Switzerland’s energy research con-cept, is co-ordinated by the Swiss Federal Office of En-ergy (SFOE). In close collaboration with various fed-eral, cantonal and municipal authorities, the pro-gramme supports research and development in thearea of hydrogen, as well as efforts to bring productsusing hydrogen technology onto the market. Theoveral funding by public institutions in this fieldsums up to $5 millions (2009), from which the SFOEcontrols roughly one quarter directly.

The general objectives of the programme are rede-fined every four years in the federal government en-ergy research concept. Fostering projects in the fieldof hydrogen production by renewable energies andhydrogen storage in solid state systems form thelong term strategy of the program. Photoelectro-chemical (PEC) water splitting, a technology thatwas pioneered in Switzerland, is one of the main ar-eas of focus in the area of hydrogen production. Thenational research activities in this field are concen-trated within a competence center PEChouse at theSwiss Federal Institute of Technology in Lausanne.The overall objective is to design and develop novelsemiconductor-based materials for efficiently con-verting solar energy into hydrogen. The area of hy-drogen storage forms a second main topic in theR&D programm primarily focussing on metal andcomplex hydrides as storage materials. Activities inthis field are highly concentrated at the Swiss Feder-al Laboratories for Materials Science and TechnologyEmpa.

Only a few new pilot and demonstrations projectscould be realized in the past. In a recent pioneeringproject an air cooled PEM-fuel cell system, that hasbeen developed at the Swiss company CEKA in col-

25

laboration with the University of Applied Science in Bi-enne and the Paul Scherrer Institute, has been inte-grated into a minibar which is operated on the Swissrailways. No other technical solution was available tosolve the power problems encountered in this appli-cation. The Sfoe is convinced that hydrogen will startto play a more and more important role and enterour energy system via niche markets where no tech-nolgoical alternatives are available.

(© CEKA AG)

More informationwww.bfe.admin.ch/research/hydrogenwww.energy-research.ch

Contact

Stefan Oberholzer, PhDSwiss Federal Office of EnergyHydrogen & Fuel Cells, Photovoltaics,Concentrated Solar PowerBundesamt für Energie3003 Bern

Phone: +41 (0)31 325 89 20e-mail: [email protected]

www.bfe.admin.ch


HYDROGEN REPORT

2

Stefan Oberholzer

26 2


HYDROGEN REPORT

Dynamisches Testen von Brennstoffzellen

Präzise Massedurchflussmesser & Regler von Vögtlin Instruments AG:

Hohe Genauigkeit dank Echtgaskalibrierung Unempfindlicher auf Kondensatbildung Grosser Dynamikbereich – geringer Druckverlust Herstellung von präzisen Gasgemischen Analoge & digitale Schnittstelle (Profibus)

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HYDROGEN REPORT

2

WEKA AG · [email protected] · www.weka-ag.ch

Sta

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Val

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Val

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� Liquid level measuring instruments for electrolysis of Hydrogen

� Process valves for production, purification and drying of gaseous Hydrogen

� Cryogenic process valves such as shut-off, control, check and relief valves

� Cryogenic couplings and componets for production and storage of liquefied cryogenic Hydrogen

� Shut-off and control valves for high-pressure (900 bar) gaseous Hydrogen

� MicroFlow valves for finedosing of Hydrogen

� Valves for high-pressure and/or liquefied cryogenic Hydrogen automotive tanks

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WEKA AG Quality Components for Hydrogen-Technology

28 2


HYDROGEN REPORT Synthetic Sapphire

28

Fig.1: Schematic diagramof the synthesis of sapphire with the process developed by Hrand Djevahirdjian

Hrand Djevahirdjian was fascinated by the publi-cation in 1902 of Prof. Auguste Verneuil's work onthe creation of synthetic ruby. Verneuil had justinvented a blowpipe using coal gas and oxygen,thereby opening up the way to industrial produc-tion. Hrand Djevahirdjian improved the process byreplacing the coal gas with hydrogen. A combina-tion of science and empiricism, it is still being usedin the plant at Monthey. The synthesis of stonesinvolves fusing alumina – with or without the ad-dition of metallic oxides – using an oxyhydrogenblowpipe and producing crystal drop by drop,much like a stalagmite, at a temperature greaterthan 2000°C.

When Hrand Djevahirdjian moved to Monthey in1914, he was determined to plan for the long term.There are currently 10’000 m2 of buildings, housingten departments: the production of refractory claymuffles, water electrolysis, the purification of am-monia alum, the calcination of the alum, the produc-tion of synthetic stones, quality control, and heattreatment, an applied research laboratory and thecompany's technical & administrative services. Dje-va has been a limited company since 1924 and cur-rently employs over 70 people. As well as manufac-turing synthetic stones for both the jewellery and in-dustrial sectors, Djeva offers a range of crystals tomeet a wide variety of needs.

The real art of synthesis behind this deceptivelystraightforward operation resides in the accuracy ofthe various settings while the crystal is growing, aprocess that can last for several hours or even days.Fusion has to be conducted continuously in the

same area of the downwardly-applied flame so thatthe crystal can be built up by the superimposition ofvery fine layers of molten material. This means thatthe pedestal has to be lowered progressively and theblowpipe fed accurately and regularly.

Alumina or aluminium oxide, the raw material forcorundum, is extracted from bauxite. Most of thiscomes from Australia and is converted into ammo-nia alum in Germany and France. Partially refined, itis then delivered to Djeva. Before the crystal makesits almost magical appearance, several preliminaryoperations have to be completed in various sectionsof the plant :• the purification of ammonia alum through recrys-

tallisation after hot-water dissolution, then filtra-tion. This process eliminates impurities which arelikely to affect the quality of the stones.

• the calcination of alum in the furnaces at temper-atures over 1100°C. Purified alum, sometimes mixed with colouring agents, is distributed into quartz crucibles to undergo thermal decomposi-tion. This operation is performed day and night. The alum is transformed into a sort of fragile meringue, which is then sieved to obtain a fine alumina powder of microscopic crystals.

• the manufacture of refractory clay muffles through pressing. Varying in diameter, these pro-tect the crystal during its growth and its cooling.

• the production of hydrogen and oxygen through electrolysis. These gases feed the blowpipes.

Within the production area, more than 2000 blow-pipes are arranged in several units. The flames arefed with a meticulously controlled supply of hydro-gen and oxygen, whilst hammers, like little tap-dancers, strike the powder drums to ensure a

Katia Djevahirdjian

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HYDROGEN REPORT

2

Fig.2: A 8 MW alkalineElectrolyzer

smooth flow of small quantities of alumina powder.This melts and progressively builds up on to the seedcrystal, giving the stone its crystalline direction. Allthat remains is to monitor the growth of the stonethrough an opening in the fire-proof oven and tocarefully regulate the operation, which ends whenthe flames are extinguished.

Hydrogen and oxygen, which feed the insatiableflames of the blowpipes, are for the most part pro-duced by water electrolysis within the company it-self. But Djeva maintains close links with outsidesuppliers to supplement its stock. On days of peakproduction, daily consumption of these gasesamounts to as much as 40000 m3. This varies, ofcourse, between day and night, and sometimes fromone hour to the next. Enjoying the benefits of mod-ern technology, the plant is presently equipped withenormous pressurised buffer tanks for storing theequivalent of approximately 20000 m3 of hydrogenand oxygen. These reserves provide the necessaryflexibility for production and consumption. Djevaconsumes around 40 GWh of electricity a year, com-parable to the needs of a village of 7500 inhabitants!This energy is mainly produced by hydroelectricplants and supplied by a nearby company. Contact details:

Katia DjevahirdjianIndustrie de pierres scientifiquesHrand Djevahirdjian S.A.Rue des Saphirs 16 . Case postale 272CH-1870 Monthey 1


www.djeva.com

Fig.3: Hydrogen and oxy-gen storage tanks

Fig.4: Series of hydrogen/oxygen furnace

30 2


HYDROGEN REPORT Hydrogen Technology in the “Self Sufficient and Sustainable Space Unit”

“Self” is a modern, self-sufficient space unit, whichis independent from external energy supply and de-signed for the purpose of living, working or study-ing in a self-sustaining way. For the energy supply,electricity is generated by photovoltaic cells, usedfor the daily purposes and stored in Li-ion batteries.Excess electricity is transformed to hydrogen by aPEM electrolyser, buffered in hydride tanks andused for cooking and heating if needed. For this pur-pose, a novel porous catalytic hydrogen burner hasbeen developed. Due to its self ignition and emis-sion-free nature, a high level of safety can bedemonstrated

“Self” is focused on advanced building technologies(Fig. 1, 2) in combination with photovoltaics (PV), hy-drogen production by water electrolysis and storageof the hydrogen via metal hydride technology. Whileelectrical energy is provided by PV and batteries andused for the electrical systems like illumination, con-trolling or computer, the focus of hydrogen is to pro-vide energy for cooking and heating purposes. Thisis advantageous compared to electrical cooking andheating systems since storage through batteries onthe timescale of months is not possible due to lowstorage density, high storage volume, safety aspectsand weight constrains.

Since the PV system and batteries are dimensionedfor stand-alone and year round operation, excesselectricity is available during summertime due toseasonal input fluctuations. This excess energy isused for producing hydrogen by water electrolysiswith a PEM electrolyser, stored in hydride tanks (Fig.3) and used for cooking and heating in wintertime .Hence, the focus is to develop a novel type of catalyt-ic H2 burner. Due to the catalytically active Pt coatingof the porous SiC ceramics, no ignition is needed (Fig.4). If hydrogen is present, heat is produced instanta-neously and thus, no accumulation without conver-sion can occur. Since the combustion of hydrogendoes not release harmful exhaust gases like CO2 or

Ulrich Vogt

Fig.3: Energy concept: Photovoltaic supply by PV, electricitystorage in batteries, Hydrogen production by water elec-trolysis and storage in metal hydride tanks

Fig.4: Principle of the catalytic H2 burner: 2H2 + O2—> H2OThe self igniting property and the fact that hydrogen andair are strictly separated, except in the catalytically activeregion, assures a very high passive safety aspect.

Fig.2: Transport of SELF by truck or helicopter to arbitrary places

U

Photovoltaics Lithium-ion battery

PEM Electrolyser Metal hydride H2 storage

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HYDROGEN REPORT

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NOx, catalytic hydrogen burners can be used indoorssafely and without risk (Fig. 5). The reaction productis only water, which is actually beneficial for theroom climate. With this project, fundamental tech-nical experience will be attained concerning stand-alone power systems (SAPs), the use of hydrogen asfuture energy carrier, the durability of PEM electrol-ysers, hydride storage systems, as well as the use ofhydrogen for cooking and heating purposes.

Contact:

Dr Ulrich Vogt, Dr Michael Bielmann, Dr Valentina Herzog, Mark Zimmermann, Prof. Dr Andreas Züttel Empa, Swiss Federal Laboratories for Materials Science andTechnologyHydrogen and EnergyÜberlandstrasse 129CH-8600 Dübendorf


www.empa.ch/h2e

Fig.1: the Self SufficientAccommodation Unit canbe transported to nearlyany place in Europe for independent living, working or research.

Fig.5: (left) Hydrogen burner with air supply system. ( right) Infrared image of the hydrogenburner at 800°C

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32 2


HYDROGEN REPORT Hydrogen sponges at home, at work, at play

Klaus Yvon

Fig.1: Hydrogen poweredlawn mower after 16years of operation. Hydrogen sponges are situated in the cylindricalcontainer.

Solid-state metal hydrides (“hydrogen sponges”)represent the safest and most volume efficientway of storing hydrogen. They have been studiedat Geneva University for over 30 years with re-spect to fundamental aspects such as synthesisand properties of new materials, and practical as-pects such as integration into practical deviceslike hydrogen storage vessels for hydrogen en-gines, fuel cell systems and home applications.

Notable achievements during the past years includethe discovery of a wide variety of so-called “com-plex” transition metal hydrides of which many arecapable of storing hydrogen in concentrations ex-ceeding that of liquid hydrogen. In a quest to putthese sponges to practical use the following hydro-gen powered devices have been designed for home, for work, and for play.

Hydrogen-powered lawn mowerGeneva has developed the worldwide first hydrogen powered lawnmower containing hydrogen spongesas a storage medium. It was adaptedfrom a commercial model running ongasoline and is one of the rare hydrogenpowered devices still operational after 17years of successful and uninterrupted use [1].

Hydrogen-powered barbecue

33


HYDROGEN REPORT

2

Pop music by hydrogenPowering a music scene represents a challenge forfuel cell systems because of the rapidly varying timestructure in energy demand of the various compo-nents (amplifier, light sources etc). In order to studythe response to such solicitations the worldwidefirst TÜF certified fuel cell system (2 kWe) was suc-cessfully tested under real conditions during the fes-tivities of the 450th anniversary of Geneva Universi-ty (Nuit de l’Université, 13 June 2009).

Solar hydrogen houseHaving evaluated a photovoltaic hydrogen produc-tion and storage installation in a residential home inSwitzerland some 9 years ago �2�, scientists atGeneva University currently are assembling an up-dated installation for solar hydrogen production,storage and utilization (stove, lawn mower, fuel cellelectricity generation), by using the latest technolo-gies available, including the use of hydrogensponges. Altogether, these applications aim atpaving the road towards the introduction of hydro-gen as a renewable energy vector in every day’s life.

Contact

Professor Dr Klaus YvonMANEP, Université de Genève24 Quai Ernest AnsermetCH-1211 Genève 4, Switzerland


www.unige.ch/sciences/crystal/yvonk/KY.html

References

[1] K. Yvon and J.-L. Lorenzoni, “Hydrogen Powered Lawn Mower: 14 Years of Operation”. Int. J. Hydrogen Energy, 31, 1763-1767 (2006).

[2] P. Hollmuller, J.-M. Joubert, B. Lachal and K. Yvon.“Evaluation of a 5 kWp Photovoltaic Hydrogen Production and Storage Installation for a Residential Home in Switzerland” Int. J. Hydrogen Energy, 25, 97-109 (2000).

Fig.2: Concentric hydrogen barbecue in use (top) and open hydrogen burners (bottom).

Fig.3: Hydrogen powered fuel cell (top)powering music scene with singerAliose (bottom) during the festivities of the 450th Anniversary of Geneva University in 2009.

A commercial barbecue has been adapted by replac-ing the propane burner by a series of hydrogen burn-ers connected to hydrogen sponges. A panel of eval-uators confirmed that the taste of hydrogen roastedmeat was undistinguishable from that of propaneroasted meat.

34 2


HYDROGEN REPORT Hydrogen for Efficiency in Conversion

Since the publication of the 2008-2009 hydrogen-report, significant advances have been achieved onall of the reported scales. Starting from an earlydemonstration of a 1 kW stand-alone system,compact and efficient fuel cell supplies forportable applications are advanced on the scalesof 1000 W, 100 W, and 1–10 W. On the other hand,fuel-cell / storage hybrid systems are developed fortransport applications. Functional vehicles such asmunicipal vehicles, standard sized cars, and light-weight family vehicles are equipped with efficientpowertrains, with the aim of launching a true in-novation in the market.

The efficient conversion of hydrogen in low-tempe-rature polymer electrolyte fuel cells at Paul ScherrerInstitut PSI dates back to 1990, when a researchgroup was formed working on fundamentals of elec-trochemistry, electrocatalysis, solid polymer elec-trolytes, and the design of fuel cell stacks and sys-tems. Together with long-term research in electro-chemical energy storage in batteries and capacitors,this know-how formed the basis for the achieve-ments mentioned below.

PowerPac – building block towards market intro-ductionBesides proven reliability and durability for the ser -vice life of the device, cost reduction of stack and sys-tem remains the main challenge for the market in-troduction of the fuel cell. Realizing two major op-portunities for cost reduction, i.e. the manufactu -ring of multifunctional bipolar plates and the poten-tial for automation of the assembly, PSI and ETHZurich joined forces in the realization of a 1 kW

portable fuel cell generator, the PowerPac. This de-vice was further developed at the UAS in Biel(http://labs.hti.bfh.ch), and found its way into fuelcell boats and a three-wheel vehicle. The companyCEKA worked on developing the PowerPac into acommercial product series (http://www.ceka.ch/Stacks.43.0.html). The stack also was at the heart ofthe PacCar vehicle.

PaC-Car – challenging the limits in fuel economyThe team around Lino Guzzella at ETH Zurich at-tacked the challenge to break the world record in fueleconomy. With a powertrain based on a PowerPacfuel cell, they designed an ultra-light weight eco-ve-hicle for one person. Due to advanced aerodynamicdesign, low rolling resistance, very low overallweight, and sophisticated controls of the fuel cellsystem, PacCar II won the prestigious trophy of the2006 Shell EcoMarathon, demonstrating a traveleddistance of more than 5000 km with the hydrogenequivalent (in energy) of one liter of gasoline.(http://www.paccar.ethz.ch/)

HY.POWER – technology platform for a family-sized fuel cell carPSI has pursued a different strategy, i.e. drastically in-creasing the fuel efficiency of family-sized cars bythe implementation of fuel cell power trains. Thefirst demonstration of a Swiss fuel cell car, theHY.POWER, was realized together with ETH Zurichand industrial partners. This was the first fuel cell ve-hicle ever to master a mountain pass, by traversingthe Simplon in winter of 2002. Based on a VW Borachassis, this technology platform demonstratedthat 40% reduction of fuel consumption was possi-ble, in spite of the weight added by the fuel cell sys-tem (http://ecl.web.psi.ch).

Hy-Light – exploring novel design options for afuel cell vehicleThe next development stage took full advantage ofthe design freedom offered by the fuel cell powertrain. In collaboration with CDM Michelin (GivisiezFR), a lightweight hybrid vehicle of 850 kg termedHy-Light was developed that offered space for fourpassengers. Its fuel cell system, fed by structure-in-tegrated hydrogen tank and an oxygen tank underthe rear seats, combined with supercapacitors forenergy recovery and peak power, excelled in 2004 bya tank-to-wheel efficiency of 60% over the drivingcycle, which resulted in a consumption equivalent to2.2 liters of diesel per 100 km. With two wheel-inte-grated electric motors, the car also demonstrated ex-cellent acceleration characteristics and driving com-fort by level control (Fig. 2). This concept has been fur-ther developed by the industrial partner.

Philipp Dietrich

Fig.1: Test with theHy.muve test-vehicle

35


HYDROGEN REPORT

2

http://www.michelin.com/corporate/actualites/en/actu_affich.jsp?id=13912&lang=EN&codeRubrique=4

Towards portable devicesRealizing the need for efficient power supplies at thescale of 100 W, teams of ETH Zurich and the PaulScherrer Institute have recently joined forces withinthe CEMTEC project, which aims at the demonstra-tion of a highly compact and efficient converter. Thefuel, butane, is converted to a hydrogen-rich feed ina partial oxidation reformer (Fig. 3). Electricity is pro-duced in a miniaturized Solid Oxide Fuel Cell that isequipped with new types of electrodes, electrolytes,and an advanced cooling concept. This project is car-ried out in the framework of the Competence CenterEnergy and Mobility, CCEM.www.ccem.ch

ONEBAT – fuel cell for the laptopGoing one step further in miniaturization, theONEBAT project team around Ludwig Gauckler ofETH Zurich aims at demonstrating a fuel cell system

with the size of a match box that will deliver severalWatts of electric power, and will hence be suitable topower portable devices such as laptops http://www.nonmet.mat.ethz.ch. With a view to ubiquitousavailability, liquid propane, the fuel used in today'sfire-ligthers , was selected, which is again convertedto a hydrogen-containing mixture in a miniaturized

reformer. An innovative element is the small-scale(1 cm2) solid oxide fuel cell which, due to the very thinceramic electrolyte of novel composition, can oper-ate at a temperature as low as 550 °C. Excellent ther-mal packaging will make sure that this hot "heart"of the device will not be felt by the outside world.This project is supported by CCEM. http://www.ccem.ch

OutlookIn one way or the other, all of the above-mentionedprojects are exploring niches where hydrogen fuelcell technology could find its way into the market.Another example is the CCEM project hy.muve [Fig. 1](www.empa.ch/hy.muve) pursued by Empa and PSItogether with industrial partners, in which a heavymunicipal vehicle is equipped with a fuel cell powertrain. This project will explore the use of fuel cells un-der heavy-duty conditions that are very differentfrom normal passenger car driving cycles. This proj-ect is described elsewhere in this brochure.

Innovation is often defined as an invention turnedinto a successful product on the market. In thatsense, intense efforts are ongoing to demonstrate afuel cell vehicle concept (including fuelling infra-structure) that could be produced in numbers reap-ing the first benefits of economy of scale, and wouldbe offered at a price that is affordable to earlymovers. Such a product would represent an impor-tant step to secure a Swiss contribution to a poten-tially very important emerging market. This is tar-geted with the collaboration of Belenos Clean Powerwith PSI and other institutes of the ETH domain.

Fig.3: Lattice-Boltzmannsimulation of 3-dimen-sional hydro-dynamicflows

Fig.2: Hy-Light car beingfuelled.

Contact

Dr Philipp DietrichCompetence Center Energy and Mobility (CCEM)c/o Paul Scherrer Institute (PSI)Managing Director CCEMCH-5232 Villigen PSI, Switzerland

Phone: +41 56 310 45 73Fax: +41 56 310 44 16e-mail: [email protected]

http://www.ccem.ch

36 2


HYDROGEN REPORT Applied Sciences on PEM - Fuel Cells in Biel

The main objective of the fuel cell group at theUniversity of Applied Sciences in Biel (BFH-TI)is to bring fuel cells to the people. Ever since asmall team of engineers started at the turn of thecentury the fuel cells activities at the BFH-TIwith the installation of a test lab for PEM fuelcells up to 10 kW, an own PEM fuel cell conceptand many demonstrators had been developed formobile applications and integrated mainly in ve-hicles. Today the BFH-TI is able to serve an ex-cellent infrastructure and high competence fordeveloping and testing PEM fuel cell systems inthe power range of some watts to several kW.

One of the larger projects was the development of afuel cell - battery hybrid system and the integrationin a lightweight electric vehicle called “SAM”. TheSAM is a three-wheel electric vehicle which offerstwo seats arranged in a row and has been developedin Biel for local traffic. The PEM-stack consists of 96cells and has a maximum power of 6 kW and in com-bination with lithium-polymer batteries the propul-sion system can be supplied by a power of 15 kW. TheHybrid SAM was tested on the roads around Biel andthe results were very satisfying: low consumption ofabout 450g H2/100km and a range of 130 km, whichseems very interesting for an urban electric lightweight vehicle.

The project is an excellent example for the fruitfulcollaboration of BFH-TI with industry and other re-search institutes. The design of the PEM-Stack, inte-grating a special internal humidification, had beenpreviously developed by PSI/ETHZ for their PowerPacand was up-scaled to a larger power. The most ex-pensive part in a PEM - fuel cell, the Membrane-Elec-trode-Assemblies (MEA), had been placed at dispos-al by Solvicore and the storage cylinders had been

developed and produced by the team of Prof. An-dreas Züttel (EMPA), which contributed their highexpertise in the field of hydrogen solid state storage.When designing a PEM fuel cell systems, there is stillone main question: shall we use air or oxygen. Todemonstrate the main differences an E-Scooter wasconverted at BFH-TI into a Fuel Cell Scooter. Hydro-gen and Oxygen are stored in 2 litres pressure cylin-ders @ 200 bar. To approve the electrical dynamics, aserious of super caps is connected directly in parallelto the PEM – Stack. The performance has beenproved through extensive tests on an inhouse cir-cuit, normally used by go-carts. As soon as pressurecylinders are availible which can be filled with apressure of 700 bar, the range will be absolutely ad-equate for urban traffic.

Driven by the motivation to tackle the problem ofhigh fuel cell costs an important strategic in houseproject was started in 2005 to develop a low-cost fu-el cell based on flexible materials, which can bepunched and promises cheep production costs evenby small scale manufacture. Instead of the solely useof conventionally milled graphite plates the new de-velopment is based on an optimal combination offoil material, which can easily be dye cut ensuringlow production time and hence cost. Further focuswas set on implementing the gas humidification in-to the individual cells and enabling a concept ofedge air cooling by providing each cell with coolingfins. Air is passed along these fins propelled by con-ventional axial ventilators.

Initial development steps were financed by theSwiss federal office of energy (SFOE). This develop-ment caught the interest of the Swiss company CE-KA AG and further development and industrializa-tion steps had been completed under the project

Michael Höckel

Fig.1: Side view of the Hybrid SAM: PEM-FuelCell and Lithium-Ion Battery and placement ofthe components in theHybrid SAM

37


HYDROGEN REPORT

2

name IHPoS (Independent Hydrogen Power Sys-tem).The IHPoS-FC stack has been developed for usewith pure hydrogen as well as reformate gas. The IH-PoS development earned Swiss acknowledgment re-ceiving the Swiss technology award 2007. The pres-entation of the IHPoS FC stack in the hall of innova-tions at the Hannover Messe, one of the biggest fairfor industrial products was a big success.CEKA AG introduced the IHPOS FC stack on the mar-ket in 2009. To demonstrate the fields of applicationof the IHPoS, the fuel cell team of the BFH-TI de-signed two different systems, the portable PemPacand the Fuel Cell Trailer with onboard generation ofelectricity by hydrogen. In the last month’s a stan-dardized modular IHPoS-System is developed with

the scope of a project, which brings together themain competences in hydrogen and PEM-fuel cellsin Switzerland and is co-financed by CTI.

Currently the IHPoS-E prototype system is been de-veloped to be integrated in a daily mobile applica-tion in the catering business. The goal is to introducea first series of IHPoS-E systems on the market by theend of 2010.

Contact

Prof. Michael HöckelUniversity of Applied SciencesDept. Engineering and Information TechnologyQuellgasse 21CH-2501 Biel, Switzerland


www.ti.bfh.ch

Fig.3: 500 W commercialPEM - fuel cell by BFH-TIand CEKA AG an typicalapplicatios

Fig.2: Typical PEM fuelCell demonstrator Systems at BFH-TI

38 2


HYDROGEN REPORT Hydrogen driven municipal vehicle (hy.muve):from the laboratory to the street

Early practical experience with fuel cell systemsand hydrogen handling is essential for policy mak-ers, vehicle manufacturer and the vehicle supplyindustry in view of the development of market im-plementation strategies, sampling of experience inreal world operation and the study of socio-eco-nomic aspects in a sensible market phase.

Fuel cell powertrains are presently being tested inpassenger cars and buses. In these sectors, success-ful market introduction faces tough challenges inview of high driving dynamics, packaging require-ments in limited space and cost expectations.Marked introduction of such vehicles is expected tobe after 2014. The hy.muve-project is aimed at the in-troduction of a fuel cell drivetrain into a municipalvehicle (road sweeper) by replacing the 55 kW dieseldriven internal combustion engine and the hy-draulic power distribution by a 20 kW fuel cell sys-tem, a 12 kWh lithium-polymer power battery and a28 kW electric motor for the traction and the electri-fication of the vacuum ventilator (Fig 1 and 2). In viewof their driving profile (operation by trained person-nel, fleet operation from a fixed refuelling point,modest driving dynamics, predominantly low part-load operation, smaller relative share of powertrainin total cost, possibility to operate such vehicles inpedestrian areas and even indoor) these vehicles ap-pear to be particularly well suited for a soon nichemarket introduction of fuel cells, and a possible earlycommercialization.

In a first project phase, Empa and PSI developed aprototype fuel cell municipal vehicle which is closeto a pre-production series in cooperation with Buch-er Schörling, the worldwide market leader in manu-facturing of municipal vehicles, Brusa Elektronik AG,a Swiss electric drive manufacturer and MesserSchweiz, a hydrogen producer and hydrogen fuelingstation manufacturer (Fig. 3 and 4). The second andactual part of the project consist of a field testing pe-riod during 18 months in Basel, St. Gallen, Berne andGeneve. During this field testing, the vehicle will beoperated by road sweeper driver in the normal fieldoperation. Thereby, the vehicle powertrain technol-ogy will be monitored by recording several data and

signals for evaluating the property changes and thegeneral technology behaviour under real world driv-ing conditions.

Municipal vehicles with their hydrostatic power-train and auxiliary drives are a new field in which fu-el cell converters have not been tested in the past. Asthe relevant components differ in specificationsfrom those of passenger cars, a chain of innovativecomponent suppliers would have an opportunity toparticipate in the market introduction of the envis-aged product. In parallel to the technical develop-ment and field testing phases in several cities, non-technical challenges for the implementation of in-novations will be identified and promising strate-gies will be developed.

On the technical side, the questions of the power-train layout with respect to efficiency, consumption,cost and spatial, thermal and electrical integrationinto a commercial vehicle represents a first chal-lenge. These questions require fundamental knowl-edge with respect to modeling, development andtesting of hydrogen based fuel cell powertrains.

A second challenge is the performance of aging anddurability studies of the fuel cell system as well ashandling and operation analysis. This part is actuallyone of the most important research fields in respectto the marked entry of fuel cell vehicles. It includesthe identification and quantification of factors thatlimits PEM fuel cell durability due to contaminationin the marked fuel, aspiration-air pollution and tech-nology disaffection using property change analysisduring the long-term testing.

Christian Bach

Fig.1: Conventional dieselengine driven powertrainfor municipal vehicles

Fig.2: Hydrogen driven hy.muve powertrain for municipalvehicles

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39


HYDROGEN REPORT

2

A third challenge is the development of an innova-tion implementation strategy for hydrogen pow-ered vehicles, which is based on socio-technologicalanalysis with the evaluation of all included actorsand the identification of barriers and risks. Suchworks have rarely been performed based on publicmid-term real world testing of fuel cell vehicles butare rather based on expert’s estimations or are doneby industrial partners without publication. There-fore, the strategy would be of interest in other re-gions with hydrogen implementation plans.

Hydrogen driven municipal vehicle are a good prac-tical exercise for certification agencies, innovativecities with visions regarding clean mobility or vehi-cle operators and service stations as well as energysupply companies. Practical experiances are impor-tant for the introduction of further hydrogen drivenpassenger vehicles like the passenger car, developedby Belenos Clean Power and PSI (see descriptionelsewhere in this report) or hydrogen driven citybusses.

Contact:

Christian BachEmpa, Swiss Federal Laboratories for Materials Science andTechnologyInternal Combustion EnginesÜberlandstrasse 129CH-8600 Dübendorf


www.empa.ch/hy.muve

Fig.3: Fuel cell system, integrated in the rear vehicle part

Fig.4: Project vehiclewith hydrogen storagebehind the driver cab, thefuel cell system and thepower battery in the rearvehicle part beyond thewaste container and theelectric propulsion motorat the front axle

40 2


HYDROGEN REPORT The hydrogen Canal Boat in Birmingham

Over the past one and a half years, the Universityof Birmingham (together with contributions fromalumni), British Waterways, Tempus, Less Com-mon Metals, and EMPA (Switzerland) have invest-ed money and materials to the value of around£100k in the design, construction, and now oper-ation of a canal boat of the future. This boat is-powered by the combination of a metal hydridesolidstate hydrogen store, a proton exchangemembrane (PEM) fuel cell, a lead acid battery stackand a NdFeB permanent magnet electric motor.

The boat, called the Ross Barlow, encapsulates veryeffectively both the hydrogen and magnetism re-search interests at the University of Birminghamand at Empa in Switzerland. Not only does hydrogenprovide the fuel for the PEM fuel cell but it also pro-vides the means (via the HD process) of manufactur-ing the NdFeB magnets.

Waterways transport is inherently efficient and theweight of the metal hydride store can be readilycompensated by the removal and redistribution ofthe existing ballast from the twelve tonne canalboat. Thus, the use of hydrogen in this context is ex-pected to become commercially viable at a muchearlier stage than in automotive applications wherethe weight and volume of the hydrogen store areboth critical factors and remain major challenges forthe future.

The PROTIUM project began with the provision of astandard maintenance boat by British Waterwaysand over the past one and a half years, the craft hasbeen converted to a passenger/display boat by re-placing the standard diesel engine with an all elec-tric propulsion system and by enclosing the middleportion of the vessel. The longer term aim is to sup-ply the boat with “green” electricity and with“green” hydrogen so that the project will becomecompletely sustainable and will have totally elimi-nated all the atmospheric, water and noise pollutionassociated with the boat. Perhaps the most novel as-pect of the Ross Barlow is the solid state store whichcontains 133 kg of powdered Ti-V-Mn-Fe alloy which,when fully charged, will store around 2.5 kg of hydro-gen (28 cubic metre at standard temperature andpressure). There are five storage units and in eachone, the metal powder is contained within sevenstainless steel tubes which are surrounded by a wa-ter jacket which provides heat when desorbing thehydrogen to the fuel cell and cooling when the storeis being charged. The temperature is maintained bymeans of a water pump and heat exchanger. Themost attractive feature of the store is that the oper-ating pressure is less than 10 bar and the 5 units to-gether store the equivalent of 4 fully charged stan-dard gas cylinders (50 liters) at a pressure of 200 bar.To our knowledge, this is by far the largest solid statehydrogen store being employed in any transport ap-plication within the UK. The Protium project, there-fore, will provide an excellent opportunity to assess

Ivor Rex Harris

Fig.1: The hydrogen powered “Ross Barlow”canal boat at the University of Birmingham.

Andreas Züttel

41


HYDROGEN REPORT

2

the performance of such a store in a working envi-ronment. Why not power the boat solely by hydro-gen? The reason is that there are advantages in em-ploying a hybrid system. One of these is that, formost of the time, the fuel cell can be employed tocharge the batteries at a steady rate and this avoidssubjecting the fuel cell to surges in demand, henceextending its lifetime. In addition, the batteries canalso be topped-up from a range of sustainable pri-mary energy sources such as wind, hydro and solar.Practically, this is much easier and more energy effi-cient than generating hydrogen from these sources.There is also some possibility of regenerative charg-

ing of the batteries. The highly efficient (~90%), hightorque, permanent magnet electric motor makesvery effective use of the energy stored in the metalhydride and in the battery stack.As stated earlier, the NdFeB sintered magnets havebeen manufactured by the Hydrogen Decrepitation(HD) process and this synergy is described in the ed-ucational material associated with the project. An-other important on-board application for NdFeBmagnets is in the guidance system where the con-ventional tiller can be substituted by a permanentmagnet actuator. The complete hybrid energy sys-tem is monitored continuously and controlled bycomputer software designed to achieve maximumefficiency and hence maximum range between therefuelling cycles.

Contact:

Prof. Rex HarrisUniversity of BirminghamBirmingham, Great Britain

e-mail: [email protected]

www.hydrogen.bham.ac.uk/protium.htm

Prof. Dr Andreas ZüttelEmpa, Swiss Federal Laboratories for Materials Science andTechnology Überlandstrasse 129CH-8600 Dübendorf, Switzerland


www.empa.ch/h2e

Fig.2: Schematic diagramof the energy flow on theboat.

Fig.3: Hydrogen storagetanks, holding 2.5 kg ofhydrogen in a metal hydride.

Hydrides

The highest volumetric densities of hydrogen arefound in metal hydrides, in some cases more thantwice the density of liquid hydrogen. Many met-als and alloys are capable of reversibly absorbinglarge amounts of hydrogen: from 1 to 3 hydrogenatoms per metal atom. The absorption takesplace using molecular hydrogen gas or hydrogenatoms from an electrolyte. The group one, twoand three light metals (e.g. Li, Mg, B, or Al) cancombine with hydrogen to form a large variety ofmetal–hydrogen complexes (e.g. Na[AlH4] andLi[BH4]). These are especially interesting be-cause of their light weight and because of thenumber of hydrogen atoms per metal atom,which is two in many cases.

Thomas Graham, from Glasgow, Scotland, was work-ing at the University College in London in 1968 whenhe exposed palladium to a hydrogen gas atmos-phere. He discovered that the hydrogen was ab-sorbed into the palladium and was able to correctlydescribe the absorption processs.

In the 1970s, Louis Schlapbach at ETH Zürich investi-gated the magnetic properties of FeTi alloys and es-pecially the effect of hydrogenation on magnetism[2]. He explained the irreversible change of the mag-netic properties of FeTi upon hydrogenation, the ac-tivation process and some surface properties of FeTiby surface segregation. In a surface layer, Ti diffusesto the surface and Fe forms magnetic precipitateswhich probably catalyze the hydrogenation. The cat-alytically active surface is renewed with each cycleof hydrogenation. Later, Schlapbach developed ex-periments and theory of hydrogen chemisorption onclean and precovered metal surfaces and applied itto techniques for preparing metal hydrides [3]. Atthe surface of hydride forming intermetallics, pre-cipitates of d metals and a metallic subsurface areproduced by surface segregation and decomposi-tion. The subsurface and the precipitates are able to

42

dissociate H2. Our recent work on the surface analy-sis of LaNi5, FeTi, Mg2Ni and ErFe2 is reviewed.

Complex transition metal hydrides constitute a rel-atively recent and somewhat exotic class of solidstate compounds. Historically, the first such com-pound and text book example is K2ReH9. It was firstreported in 1964 and found to contain tricapped trig-onal prismatic [Re(VII)H9]2- complex anions inwhich rhenium is fully oxidised. The second member,Sr2RuH6, was reported in the 1970s and was found tocontain an octahedral [Ru(II)H6]4- complex. Wider in-terest in these compounds formed in the 1980s afterthe discovery of transition metal hydrides (most ofwhich are metallic), such as LaNi5H6 and FeTiH2,which have now reached commercial maturity forreversible hydrogen storage in batteries for portableelectronics (mobile phones, laptops, etc.). One ofthese compounds, however, is non-metallic(Mg2NiH4) and shows a nearly fixed hydrogen con-tent. This compound was classified as a complextransition metal hydride after its structure had beenfully characterised and found to contain discretetetrahedral [Ni(0)H4]4- complexes. This triggered in-tense activity in the field and led to the discovery of

2


HYDROGEN REPORT

Fig.1: Lennard-Jones potential of hydrogen ata metal surface.

Andreas Züttel

many other homoleptic hydride complexes, such asoctahedral [FeH6]4-, square-pyramidal [CoH5]4-,square-planar [PtH4]2-, and linear [PdH2]2-. A signifi-cant part of that work was performed by the groupof Klaus Yvon [4] at the University of Geneva.

After the first report of reversible hydrogen sorptionon catalyzed Na[AlH4] at temperatures of 180°C and210°C by Bogdanovi� and Swickardi in 1996, AndreasZüttel [5] at the University of Fribourg suggested thestable compound LiBH4 as a similar alternative. Ithas the highest gravimetric hydrogen density atroom temperature known today (18 mass%). Thisclass of complex hydrides could be the ideal hydro-gen storage material for mobile applications. LiBH4desorbs three out of every four hydrogen atoms in

the compound upon melting at 280°C and decom-poses into LiH and boron. Although there was at firsta lot of doubt about the reabsorption of hydrogen inboron compounds by chemists around the world,numerous groups worldwide work intensively onborohydrides for hydrogen storage today.

43

References

[1] Thomas Graham „On the Occlusion of Hydrogen Gas by Metals“, Proc. Royal Soc. 16 (1868), pp. 422

[2] L. Schlapbach, A. Seiler and F. Stucki, “Surface segrega-tion in FeTi and its catalytic effect on the hydrogena-tion”, Materials Research Bulletin, Volume 13, Issue 7, July 1978, pp. 697-706

[3] L. Schlapbach, A. Seiler, F. Stucki, H.C. Siegmann , “Surface effects and the formation of metal hydrides”, Journal of the Less Common Metals, Volume 73, Issue 1, 1September 1980, pp. 145-160

[4] K. Yvon, “Complex Transition Metal Hydrides”, Chimia 52:10 (1998), pp. 613-619

[5] A. Züttel, P. Wenger, S. Rentsch, P. Sudan, Ph. Mauron, Ch. Emmenegger, “LiBH4 a new hydrogen storage material”, Journal of Power Sources 118 (2003), pp. 1–7


HYDROGEN REPORT

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Contact

Prof. Dr Andreas ZüttelEmpa, Swiss Federal Laboratories for Materials Science andTechnology Dept. Environment, Energy and MobilitySect. 138 “Hydrogen & Energy”Überlandstrasse 129CH-8600 Dübendorf, Switzerland


www.empa.ch/h2e

Fig. 2 Isotherm of hydrideformation

Fig. 3 Selected borohy-drides

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HYDROGEN REPORT Hydrogen Facts

Hydrogen — (Gr. hydro, water, and genes, forming).Hydrogen was prepared many years before it wasrecognised as a distinct substance by Cavendish in1766, it was named by Lavoisier (1). Hydrogen is themost abundant element in the universe, and it isthought that the heavier elements were, and stillare, built from hydrogen and helium. It has been es-timated that hydrogen makes up more than 90% ofall atoms or three quarters of the mass of the uni-verse. Hydrogen is found in the sun and most stars,and plays an important part in the proton-proton re-action and carbon-nitrogen cycle, which accountsfor the energy of the sun and stars. It is thought thathydrogen is a major component of the planet Jupiterand that at some depth in the planet's interior, thepressure is so great that solid molecular hydrogen isconverted into solid metallic hydrogen. In 1973, itwas reported that a group of Russian researchersmay have produced metallic hydrogen at a pressureof 2.8 Mbar. At the transition, the density changedfrom 1.08 to 1.3 g/cm3. Earlier, in 1972, a Livermore(California) group also reported a similar experi-ment in which they observed a pressurevolumepoint centered at 2 Mbar. It has been predicted thatmetallic hydrogen may be metastable; others havepredicted it would be a superconductor at roomtemperature.

On earth, hydrogen occurs chiefly in combination-with oxygen in water, but it is also present in organicmatter such as living plants, petroleum, coal, etc. It

is present as a free element in the atmosphere, orig-inating from water splitting by UV-light, but only tothe extent of less than 1 ppm, by volume. It is thelightest of all gases and combines with other ele-ments, sometimes explosively, to form compounds.Great quantities of hydrogen are required commer-cially for the fixation of nitrogen from the air in theHaber-Bosch ammonia process and for the hydro-genation of fats and oils. It is also used in large quan-tities in organic chemistry e.g. in methanol produc-tion, hydrodealkylation, hydrocracking, and hy-drodesulfurization. It is also used as a rocket fuel, forwelding, for production of hydrochloric acid, for the

reduction of metallic ores, and for filling balloons.The lifting power of 1 m3 of hydrogen gas is about1.16 kg at 0°C and 1 bar pressure.

Tempera - Vapor Density [kg/m3]ture [K] pressure

[kPa]�pS �pL �pG

1 11·10-37 89.0245 4.76·10-3 88.96510 255.6 88.136 0.00612 1837 87.532 0.03713.803a 7.0 86.503 77.019 0.12620 93.5 71.086 1.24720.268b 101.3 70.779 1.33830 822.5 53.930 10.88732.976c 1293 31.43

Production of hydrogen worldwide amounts 2006to more than 50 million metric tonnes per yea (2). Itis prepared by the reaction of steam on heated car-bon, by thermal decomposition of certain hydrocar-bons, by the electrolysis of water, or by displacementfrom acids by certain metals. It is also produced bythe reaction of sodium or potassium hydroxide withaluminum. Liquid hydrogen is important in cryogen-ics and in the study of superconductivity, as its melt-ing point is only 20 K.

The ordinary isotope of hydrogen, H, is known as pro-tium. In 1932, Urey announced the preparation of astable isotope, deuterium (D), with an atomic weightof 2. Two years later an unstable isotope, tritium (T),with an atomic weight of 3 was discovered. Tritiumhas a half-life of about 12.5 years. One atom of deu-terium is found in about 6.000 ordinary hydrogenatoms. Tritium atoms are also present but in muchsmaller proportion. Tritium is readily produced in nu-clear reactors and was used in the production of thehydrogen bomb. It is also used as a radioactive agentin making luminous paints and as a tracer.

The current price of tritium, to authorised personnel,is about 2 Euro/Ci. Deuterium gas is readily available,without permit, at about 10.000 Euro/kg. Heavy wa-ter, deuterium oxide (D2O), which is used as a mod-erator to slow down neutrons, is available withoutpermit at a cost of around 500 Euro/kg, dependingon quantity and purity. The price of hydrogen is di-rectly bound to the price of electricity (0.05Euro/kWh) and therefore around 2.5 Euro/kg.Quite apart from isotopes, it has been shown thathy-drogen gas under ordinary conditions is a mixture oftwo kinds of molecules, known as ortho- and para-

Fig.1: Primitive phase diagram for hydrogen

Tab. 1: Vapor pressure and density of p-hydrogen at lowtemperatures, a Triple point, b101.3 kPa, cCritical point.

Andreas Züttel

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HYDROGEN REPORT

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hydrogen, which differ from one another by thespins of their electrons and nuclei. Normal hydrogenat room temperature contains 25% of the para formand 75% of the ortho form. Consideration is beinggiven to an entire economy based on solar- and nu-clear-generated hydrogen. Located in remote re-gions, power plants would electrolyze sea water; the

hydrogen produced would travel to distant cities bypipelines. Pollution-free hydrogen could replace nat-ural gas, gasoline, etc., and could serve as a reducingagent in metallurgy, chemical processing, refining,etc. It could also be used to convert organic waste in-to methane and ethylene.

References:

(1) Charles T. Lynch, CRC Handbook of Materials Science: General Properties, 1974

(2) M. Richards, A. Shenoy, H2-MHR pre-conceptional design summary for hydrogen production, Nucl Eng Technol 2007, 39, 1-8

Tab. 2: Combustion andexplosion properties ofhydrogen, methane,propane and gasoline.a100 kPa and 15.5°C. bAverage value for a mixture of C1-C4 andhigher hydrocarbons including benzene. cBasedon the properties of n-pentane and benzene. d Theoretical explosiveyields.

Fig.2: Effect of temperature on flammability limits of hydrogen in air (pressure100 kPa).

Fig.3: Flammability anddetonability limits of thethree component systemhydrogen-air-water a)42°C, 100 kPa; b) 167°C,100 kPa, c) 167°C, 800 kPa

Hydrogen Methane Propane GasolineDensity of gas at standard conditions [kg/m3(STP)] 0.084 0.65 2.42 4.4a

Heat of vaporisation [kWh•kg-1] 0.1237 0.1416 0.07-0.11Lower heating value [kWh•kg-1] 33.314 13.894 12.875 12.361Higher heating value[kWh•kg-1] 39.389 15.361 14.003 13.333Thermal conductivity of gas at standard conditions [mW•cm-1 K-1] 1.897 0.33 0.18 0.112Diffusion coefficient in air at standard conditions [cm2•s-1] 0.61 0.16 0.12 0.05Flammability limits in air [vol%] 4.0- 75 5.3-15 2.1-9.5 1-7.6Detonability limits in air [vol%] 18.3-59 6.3-13.5 1.1-3.3Limiting oxygen index [vol%] 512.1 11.6b

Stoichiometric composition in air [vol%] 29.53 9.48 4.03 1.76Minimum energy for ignition in air [mJ] 0.02 0.29 0.26 0.24Autoignition temperature [K] 858 813 760 500-744Flame temperature in air [K] 2318 2148 2385 2470Maximum burning velocity in air at standard conditions [m•s-1] 3.46 0.45 0.47 1.76Detonation velocity in air at standard conditions [km•s-1] 1.48-2.15 1.4-1.64 1.85 1.4-1.7c

Energyd of explosion, mass-related [gTNT/g] 2411 10 10Energyd of explosion, volume-related [gTNT•m3(STP)] 2.02 7.03 20.5 44.2

2

Contact

Prof. Dr Andreas ZüttelEmpa, Swiss Federal Laboratories for Materials Science andTechnology Dept. Environment, Energy and MobilitySect. 138 “Hydrogen & Energy”Überlandstrasse 129CH-8600 Dübendorf, Switzerland


www.empa.ch/h2e

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IndustryAccaGen SA Mezzovico www.accagen.comCEKA Elektrowerkzeuge AG + CO. KG, Bereich B Wattwil www.ceka.chCommune de Monthey, Service Industrielle Monthey 1 www.monthey.chDiamond Lite S.A. Thal www.diamondlite.comDJEVAHIRDJIAN H. S.A. Monthey www.djeva.chH. Bieri Engineering GmbH Winterthur www.bieri-ing.chIndustrie Haute Technologie SA Monthey www.iht.chLinde Kryotechnik AG Pfungen www.linde-kryotechnik.chMichelin Recherche et Technique SA Givisiez www.michelin.chNova Werke AG, Hochdrucktechnik Effretikon www.novaswiss.chOffice de la circulation et de la navigation de FR ( OCN ) Fribourg www.ocn.chRadiamon SA Puidoux-Gare www.radiamon.chS-ce Simon consulting experts Zürich www.s-ce.chScience Solutions Baden www.sciencesolutions.chSwiss Federal Office of Energy (SFOE) Bern www.bfe.admin.chWEKA AG Bäretswil www.weka-ag.ch

Research and EducationEmpa, Hydrogen & Energy Dübendorf www.empa.ch/h2eEPFL, Institut des sciences et ingénierie chimiques Lausanne www.epfl.chHaute Ecole d'Ingénierie et de Gestion du Canton de Vaud (heig-vd) Yverdon www.heig-vd.chHES-SO/Valais-Wallis Sion www.hevs.chHochschule für Technik und Informatik HTI Biel www.ti.bfh.chHochschule für Technik+Architektur HTA Luzern Horw www.hslu.ch/technik-architekturnovatlantis c/o Competence Center Energy and Mobility CCEM Villigen www.novatlantis.chPaul Scherrer Institut (PSI) Villigen www.psi.ch

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