A Review of Hydrogen and Fuel Cell Related Research Activities in Turkey

Figen KadirganChemistry Department, Faculty of Science,

Istanbul Technical University, Istanbul/Turkey

kadirgan@itu.edu.tr

OUTLINE

•Hydrogen and Fuel Cells Technologies National Program

•Projects related to H2 and FCs in TURKEY

•Projects in Istanbul Technical University

• Turkey has announced the National Research and Technology program (Vision 2023). The objective of this project is the formulation of a strategy document for new national science and technology policies and the establishment of the priority areas. Vision 2023 is the latest finalized national project thatincludes an outline of critical technologies to be studied and developed in Turkey during the years 2003-2023. The objective of the Vision 2023 project is the formulation of a strategy document for new national science and technology policies and the establishment of priority areas. This strategy document was finalized on the 10th of March 2005.

• Within the umbrella of this RD&D program, a high priority is assigned to “Hydrogen and Fuel Cells Technologies” and the implementation plan is in progress and planned to finalize by the year of 2006. Environmental and Energy Technologies is one of the sub-national critical program areas. Within this scope a high priority is assigned to “Hydrogen and Fuel Cells Technologies National Program”.

• Nevertheless, an additional 500 million USD has been allocated to support the R&D projects in the fiscal years 2005 and 2006.

• In recent years, there have been very promising progress on H2&FC activities within the frame of national and international level with respect to private-public partnership including research institutes, universities and industries. It is extremely necessary to co-ordinate the activities of various actors such as research institutes, universities, industries and policy makers in national level in a good way with a close interaction from EU. That is the reason; these cooparations are highly encouraged and formulated within the program planned.

• Whilst the National Program has been a useful initiative, real added value will be realized in the future implementation. The current implementations show that besides the national sources, EU Framework programmes and other international collaborations are going to be crucial for efficient use of human resources and allocated budget. Success of this program will also create a significant added value for European platform.

• The budget of the on-going national hydrogen and fuel cell projects amounts to over ten millions euros.

•In this talk, a review of hydrogen and fuel cell related research activities in Turkey will be summarized. The scientific programme of Turkey may be considered on 5 groups:

•First group is concentrating on production of hydrogen via conversion of hydrocarbons (such as natural gas, coal or alcohols) or via electrolysis using environmentally friendly energy sources, •Second group is focusing on the ways, approaches and media for hydrogen storage and transportation. •Third group is working combustion of hydrogen either by mixing with another fuels or in various fuel cells; with application in portable, vehicles, stationary or residences. •Forth group is concentrating on the computer modelling, simulation of virtual elements of the system and system integration. •Finally the role of clean energy in sustainable development concept and acceptance of alternative energy resources by society, safety and standard issues are investigating by other groups.

Some on-going projects related to H2 and FCs in TURKEY

Hydrogen Production• In Middle East Technical University, studies on hydrogen are composed ofbiological hydrogen production, fuel cell applications and hydrogen storage. Amulti-discipline research on biohydrogen production is going on. Currently the major portion of this biohydrogen group’s work is focused on the scale upand outdoor operation of the existing systems since it is the vital step towardsthe assessment and implementation of industrial biohydrogen.A second global target of biohydrogen studies is the investigation and

manipulation of the biological hydrogen mechanisms. State-of-the-art, fastand efficient techniques are applied for probing deeper into the metabolicstructure. Specified works include studying biochemical and geneticcharacterization of hydrogenases from photosynthetic microorganisms; biotechnological hydrogen production from organic acids and biomass; and bacterial molecular genetics.• In VESTEL company studies on hydrogen are composed of reforming of natural gas and LPG by catalytic way and also hydrolysis of sodium bor hydride.

Hydrogen Production

• Development of PEM electrolysers (Theorytical Modelling Works)

• Development of bifunctional (regenerative) fuel cells (Istanbul Technical University –Sofia Academy of Science), Development of new electrodes and investigation of electrode reaction kinetics with participation of gases as reactants excluding fluid water.

• Hydrogen production from diesel

Hydrogen Storage and Transportation

• Storage in various metal hydride beds (Mg based thin films, Mb-B-Al based storage tanks

• Storage in carbon nano tubes (ITU)

Fuel Cells

• PEM fuel cells (H2-O2 , direct alcohols, direct boron hydride)

• Solid oxide fuel cells• Molten carbonate fuel cells• Alkaline fuel cells

System integration

• Stack design (UNIDO – ICHET, MAM)• Modelling studies

An Overview On The Fuel Cell Studies Made In Istanbul Technical University

• Direct Alcohol Fuel Cells - a high energy density – liquid at ambient temperatures– safe storage and handling

• H2-O2 fuel cells(up to 1% CO containing H2 is using as fuel)• Main problems;• The low activity of alcohol or H2 oxidation catalysts, cost• The phenomenon of alcohol crossover through the polymer

electrolyte membrane from the anode to cathode side as a consequence low activity of air catalyst

• Cost of membrane

Solution

• Development of new anode and/or cathode catalysts

• Development of alcohol impermeable membranes

• Development of new membranes

• Preparation of bimetallic electrodes (such as Pt/Ru, Pt/Sn, Pt/Mo on different supporting materials such as C or diamond) and ad-atoms to give improved activity for the fuel oxidation and decrase of the cost

• Use of electron conducting polymer as matrix, such as polyaniline, polypyrrole or polythiophene, also allows dispersing electro-catalytic materials at the molecular level in such a way that the reactive molecules will easily reach the catalytic centres.

• Preparation of nano dispersed chalcogenides as methanol-tolerant oxygen reduction catalysts(Carbonyl or phthalocyanine complexes of metals).

• Modification of Nafion by poly pyrolle

•Comparison of the oxygen reduction reaction at 250C, 0,1M HClO4, 5 mV.s-1 a) E-TEK 20% Pt/C catalyst, b) Vulcan XC-72 supported MoxRuySez catalyst, c) PANI modified E-TEK 20% Pt/C catalyst ,d) PANI modified Vulcan XC-72 supported MoxRuySez catalyst(S.Sari Ozenler, F. Kadirgan, (2006), Journal of Power Sources, 154, 364-369.)

-0,2 0,0 0,2 0,4 0,6 0,8 1,0

-14

-12

-10

-8

-6

-4

-2

0

2

d)

c)

b)a)

i d (mA

.cm

-2)

E (V)

Comparison of the oxygen reduction reaction at 250C, 5 mV.s-1 in 0,1M HClO4 + 1 M CH3OH , a ) Vulcan XC-72 supported MoxRuySez catalyst, b) E-TEK 20% Pt/C catalyst c) PANI modified E-TEK catalyst , d) PANI modified Vulcan XC-72 supported MoxRuySez catalyst,

-0 ,2 0 ,0 0 ,2 0 ,4 0 ,6 0 ,8 1 ,0-8

-7

-6

-5

-4

-3

-2

-1

0

1

d )

c )

b )a )

i d (mA

.cm

-2)

E (V )

Diffused methanol concentration in function of time on modified and non-modified membrane

~ 5.8x10-7mol-6 gün sonra

-~10-2mol96h saat sonra

~ 4.5x10-7 mol~10-4

mol24h saat sonra

-~ 10-5molAfter 14h

Modifiye NafionModifiye edilmemişNafion

Crossover rate of methanol

~1.47x10-12-1.49x10-12After 6 days

-~3.69x10-8-After 96h

~6.63x10-12~1.47x10-93.51x10-12After 24h

-~2.53x10-10-3.43x10-10After 14h

ModifiedNafion

Non-modifiedNafion

ModifiedNafion

Non-modifiedNafion

Crossover rate calculated from Gas Chromatograpy

(mol/cm2.s)

Crossover rate calculated from I-V curves

(mol/cm2.s)

Time at open circuit potential conditions

Estimated R values for modified Nafion (kΩ)

2,68 (kΩ)700 C

43,6 (kΩ)300 C

• These preliminary results confirm the interest of modification of Nafion by poly (1-methyl pyrrole) by electrochemical deposition for DMFC applications.

• (F. Kadırgan, O.Savadogo, (2004). An electroanalytical study of methanol crossover through nafion 117 membrane, IEEE, Fuel Cell Science, Engineering and Technology - 2004, 129-132.

• F. Kadırgan, O.Savadogo, (2004) R. Journal of Electrochemistry)

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