This paper is an historical essay on development of fuel cell technologies in Ukraine and short description of the National Program on Fuel Cells. It is shown that fuel cell technologies have both many years positive experience in Ukraine owing to Oganes Davtjan's efforts since early 50th of the 20th century, which were interrupted by political events in the 70th, and opportune perspectives based on achievements determining these up-to-date high technologies like nanosized zirconia and other oxide powders, materials for interconnects and microturbines, production of hydrogen, gasification of coal as well as own zircon-sand and scandium ore deposits, well-developed manufacture of gas turbines and another energetic components and equipment.
Fuel cell is an energetic technology, which is revolutionizing energy consumption. People have to understand that taking hydrocarbon fuels for production of heat or electricity with traditional ways they are able to use roughly only one-third part of energy stored in the fuel, and the rest of it is simply lost. It means that people might be satisfied with only one third of all organic fuels used at present. Fuel cells, especially their solid oxide and molten carbonate types, give the unique possibility to use that lost part of energy in a very flexible form namely electricity. Except significant saving of energy the fuel cells diminish seriously harmful pollutions typical for power stations and transport based on internal-combustion engines. Here, one Ciceronian example is worthy to be mentioned. When Daimler Chrysler was asked about their vision of future, their answer was as the next: "Anticipating future demands, DaimlerChrysler is already today operating a large number of fuel-cell-powered vehicles in successful practical endurance tests" that was accompanied by the nice symbolic picture of a humming-bird drinking water from the car exhaust pipe .
Figure 1. O.K. Davtjan together with his wife and colleague E.G. Mysyuk.
While not offering a specific date, the former US vice-president Al Gore said that advances in fuel cell technology and research led him to believe the gasoline engine could be replaced (by fuel cell engine – author) before 2017. He has anticipated that fuel cell technologies will reduce the US consumption of foreign oil, clean air, and ultimately make roads safer . The developed countries are actively elaborating numerous technologies concerning fuel cells and put already them on commercialization way for manifold applications. And what about Ukraine? Strictly speaking about today situation, the expression "near zero" is very generous estimation. And what about the past? What is history of this topic in Ukraine? The work on the National Fuel Cell Program initiated by me as a person, who came out from the field of structural zirconia ceramics, has brightly displayed the very dramatic and emotive story that is worthy to be put in the base of cliffhanger novel or movie. My the best knowledge is saying that the beginning of Ukrainian fuel cells was put by eminent famous and esoteric Armenian and Ukrainian scientist Prof. Oganes Davtjan (1911-1990, Fig. 1) in 1953 at Mechnikov Odesa State University at Chair of Physical Chemistry.
Oganes Davtjan is the Father of Ukrainian Fuel Cells; Ukrainian Fuel Cells were born in Odesa. Oganes Karapetovych Davtjan was born in Armenia, in Akhurjan village, on April 15, 1911. His education he obtained at Yerevan and Moscow Universities. His PhD degree in chemistry Oganes Davtjan obtained in 1938 at Moscow Oil Institute for his work "Theory on Association of Molecules". His activity was continued in Moscow Energetic Institute where Davtjan obtained his doctor's degree on Technical Science in 1944 for work "Problems of direct transformation of chemical energy of fuel into electricity". In 1947, Davtjan published his book under the same title, which was the first book on fuel cell theory and technology in the World . Since 1945, after a few years of knocking about the former Soviet Union (after Moscow, Davtjan worked in Kazan', Yerevan, and Vilnius where he suffered on political persecutions for quantum chemistry, which was "bourgeois" science like "prostituting girl of imperialism" in Soviet Union in that time), Oganes Davtjan got at least the chair for physical chemistry at Odesa University in 1953, July 3, where he initiated the works on fuel cells ("Davtjan's elements"). His activity was strongly supported by Ukrainian government under Petro Shelest by the special act N67 (January 20, 1962) on foundation of special laboratory for fuel cells. In contrary to the today government the funding was huge; it allowed building of special laboratory, design bureau, workshops etc. Davtjan has dealt with solid oxide, molten carbonate, and alkali fuel cells. Since that the laboratory under Davtjan has developed as follows:
Cheap catalysts for hydrogen and oxygen electrodes based on oxides of La, Co, Ni, Ti etc;
Design and technology of hydrogen and oxygen electrodes;
Design of fuel cells stock and technology of its manufacture;
Automatic control of fuel cell stock.
It is worthy to be noted, Davtjan's team has made the 200 W hydrogenoxygen alkali fuel cell stocks in 1962 (Fig. 2). Temperature of working gases was 170 °C; their pressure was 20 atm. They have developed the fuel cells that could operate at 700 C with a solid ionic conductor as electrolyte too. Davtjan added monazite sand to a mix of sodium carbonate, tungsten trioxide, and soda glass "in order to increase the conductivity and mechanical strength". Broers and Katelaar tested the Davtjan’s electrolyte in 1960, and established that this electrolyte has two phases, a molten phase consisting of carbonates, phosphates, tungstates and silicates, and a solid phase based on rare earth oxides . Since that 1 kW and 5 kW stocks, which did not require noble expensive metals, were developed and made for atomic power stations to dump peak loads. The Davtjan's progeny put them in the basement of hybrid engines for vehicles (fuel cells á inner-combustion engine) in cooperation with Yerevan, Armenia, and Cherkasy, Ukraine. For his work in the field of fuel cells Oganes Davtjan was nominated by the Czech Academy of Science for the Nobel's Prize. Unfortunately their efforts were not understood and not supported. The reader may find more details about the activity of Oganes Davtjan in the fuel cell field in .
Figure 2. The Davtjan's 200 W hydrogen-oxygen alkali fuel cell stock.
Except of Ukrainian fuel cells Prof. Oganes Davtjan is the founder of quantum chemistry in the FSU and the author of the first Soviet manual on quantum chemistry published by him in 1962. Since 1968, when O. Davtjan left Odesa for Yerevan, he had no more possibility to continue his experimental work in the fuel cell field. Having a very wide spectrum of devotions, Davtjan had concentrated on theoretical physics and, as a result, he has created the universal "The Theory of the Fundamental Field", which is finally concluding the model of Universe and existing the God as the Supermind of the Universe . It is very important that O. Davtjan is considering the fuel cell effect as a base of human intellectual and motional activities, supposing that, e.g., phosphorus and oxygen reacting in the adenosine three-phosphate molecules of body cells and neurons produce electricity and mechanical movement. The metastable adenosine three-phosphate molecules decompose into stable adenosine two-phosphate molecules and phosphate ions. "The efficiency of this transformation is the highest like in fuel cells" . And now briefly about modern Ukrainian fuel cell history: Being based on many years positive experience in manufacture of real nano-sized zirconia powders with different stabilizers like yttria, calcia, scandia etc. and zirconia ceramics [8, 9] the first Ukrainian demonstrating model of zirconia fuel cell was made and exhibited by January 22, 2002 [10- 12]. It has realized 0.85 V and 0.5 V of electro motive forces with propane gas and ethanol respectively at their direct burning.
Figure 3. Structure of the first Ukrainian thin film zirconia ceramic fuel cell transformer. Left part of the picture shows the LSM cathode of around 10 μm thickness and its surface followed by the dense solid YSZ electrolyte of 60-70 μm thickness with a few isolated pores; the right part shows the highly porous zirconia–Ni anode. Scanning electron microscopy, Superprobe 733, JEOL.
Now, under auspices of the Ukrainian Parliament the National Program "Fuel cells" for 10 years period is developed . The Program is considering fuel cells based on zirconia as very perspective for Ukraine taking into account its significant natural advantages. They are the most effective and reliable. They do not need in noble metals and may utilize practically all the types of organic fuel. Polymeric proton exchange membrane fuel cells will be developed for a few applications too.
The goal of the “Fuel Cells” Program is consolidation of efforts of Ukrainian society for accelerated development of fuel cell technologies. Its launch is caused by need of significant improvement of efficiency of organic fuel consumption especially natural gas and oil, transition to prevailing use of synthetic gas from coal at production of electric energy; sequestration of pollutions like CO2, NOx, SOx etc. produced with power plants and internal combustion engines (ICE). Fuel cells stimulate a development of related branches of economy like fine technical ceramics, transport etc. The Program “Fuel Cells” is self-developing. It consists of eight separate interdependent blocks. It is like a scheme of roads-directions, moving along them it is possible to reach the final goal. The first its “building block” is the Scientific & Technological Program “Fuel Cell Technologies”, which must determine the next steps of development of the Program as a whole.
Analysis of condition of development of fuel cell technology in the World and Ukraine shows that the difference between Ukraine and other developed countries exists, but this difference is not so significant from the point of view of scientific and technological achievements. The most drastic is the difference in their practical application. But it might be quickly worked out, if scientific and industrial forces would be combined and financially supported in right way. The National Program “Fuel Cells” is directed on removing the gap between different scientific achievements and uniting them in elaboration of fuel cell technologies and their utilization. The blocks of the National Program "Fuel cells" are as follows (Fig. 4):
Fuel Cell Technologies. This Academic Scientific & Technological Program is the starting block of the National Program, according to which samples of fuel cells, systems for fuel conditioning will be worked out; their test and optimization will be achieved during five years. During this time the other blocks of the National Program will be elaborated and their relationships will be coordinated. Market research will be performed and relationships with other developed countries in the World will be established. Scientific meetings and efforts directed on creation of favorable public opinion will be done routinely.
Fuel Cells Manufacture. The development and manufacture of several types of fuel cells for production of electric and heat energy to meet decentralize and centralize power supply of different power are planned. The special attention is given to zirconia ceramic fuel cells to supply residencies by electricity and heat; to replace internal combustion engines in different transport applications; to work in hybrid pairs with wind and solar generators, and gas turbines; for production of oxygen for medical needs etc.
Figure 4. Structure of the Ukrainian National Program "Fuel Cells".
Ceramic Industry. The success in development of zirconia ceramics leads to the development of the whole fuel cell technology, which was taking place during the last 100 years, from time of discovery of “the Nernst's mass”, which were zirconia base compounds. The typical strength of Ukrainian “ceramic steel” is around 1 GPa that allows thinning it to micron thickness . Many people are familiar with Ukrainian ceramic scalpels, which not only improves the quality of surgery, but also speeds the healing of wounds. Here Ukraine has the possibilities of supplying the population by surgical tools of new generation, avoiding the stage of production of metal scalpels, which Ukraine never had. Special place in this list of goods takes thermal barrier coatings, without which the improved performance of modern gas turbines, which blades are usually coated by thin layers of protective zirconia ceramic coating, would be impossible.
Fuel Cell Energy Systems for Centralize and Decentralize Power Supply. Several energy systems for residential and centralized power supply of different power must be developed and manufactured. Among them there are systems, which may be used together with solar and wind generators of comparatively small power to avoid the primary weakness of these ecologically pure generators, namely their intermittence that does not allow to produce energy on demand. High temperature reversible SOFCelectrolyzer may be used effectively instead of internal combustion engines and electric accumulators making generators from these renewable energy sources really ecologically pure and reliable. These reversible systems will promote to wider spreading of utilization of renewable energy.
Gasification of Coal and Waste. Gasification of coal is one of the main technologies, which produces the gas for further production of electricity by fuel cells or for other applications. The research should be carried out also for finding the best way to obtain gas from low caloric coal with substantial content of sulfur and also from fuel mixtures, such as biomass or from enriched waste. In Ukraine, scientists of Scientific Center of Coal and Energy Technology and Design Bureau “Pivdenne” have already worked out the technology of gasification of Ukrainian coals. Preliminary tests have indicated the possibility of building fuel cell electric power station with power of blocks of 10 MW, which will have effectiveness of transformation of coal energy into electricity of 65%, compared to existing 34-46% for thermal power stations.
Hybrid of Fuel Cells and Gas Turbines. Today the research efforts in Ukraine are concentrated on fuel cells and gas turbines separately. The combination of these two devices may propose a substantial economic benefit through the increased effectiveness of fuel consumption from 50 to 80% with reducing the emission of nitrogen oxide and CO to 2ppm along with the reduction of the financial investment by 25% over one fuel cell system. The combination of Ukrainian gas turbines manufactures by “Zorya” Plant, Mykolayiv, and coated with Ukrainian Electron-Beam ceramic thermal barrier coating along with zirconia ceramics fuel cells will allow the double efficiency of transformation of fuel energy into electricity and reduce the emission of CO2 by 30% in comparison with the best gas turbine at simultaneous reduction of cost in production of electric power.
Utilization of hydrogen sulfide. Zirconia ceramic fuel cells are the ideal means to use hydrogen sulfide as a fuel for production of heat, electricity, and value industrial substance −sulfur. Zirconia ceramic fuel cells are reliable in contact with sulfur-containing substances; they may produce electricity in the full analogy with pure hydrogen or organic fuels. Ukrainian scientists from National Polytechnic University (Kyiv) have developed ecologically pure technology of yield of hydrogen sulfide from Black See. This work will promote both production of value energy and substance, and purification of ecologically dangerous Black See.
Fuel Cells for Transport and Transport with Fuel Cell Engines. The wide use of transportation devices with fuel cells would be able to influence positively on reduction of consumption of oil products and minimizing the emissions over dense populated areas. International experience is quite positive here. Fuel cells potentially may substitute the internal combustion engine for all transportation devices, because they have higher effectiveness, much less pollution’s and they are able to work on different fuels, such as hydrogen, ethanol, methanol, or natural gas. In Ukraine, as it was mentioned above, scientists have already created the acting samples of electric automobiles, which may be used as a base for testing of fuel cell engines and creation of an industry of transponrt means of new generation.
Finally, the National Program “Fuel Cells” is directed on development in Ukraine the economical and ecologically safe alternative to nuclear power engineering namely based on fuel cells, industry of technical ceramics and transport means including cars of new generation that will allow in general to cut consumption of gas for 30-50% and reduce its price for 20-30% at production of electric energy only, increase significantly consumption of coal to replace natural gas, significantly cut pollution in atmosphere including CO2 for 50% and create hundreds thousands of new high technological working places.
Advantages from realization of the Program might be as follows:
Reliable provision of high quality electrical energy;
Reduction of transportation costs, using electricity and heat for industrial processes and air conditioning at the place of its production;
Avoiding losses in peak load and voltage;
Production of electrical energy in areas with very sensitive environment;
Flexibility in choice of variety of fuel and power;
Finally, electrical energy will be cheaper;
Production of doubled amount of electric energy from the same amount of fuel;
Reducing capital expenses and risks due to flexibility of power and location of station, fast building and starting of module fuel cell system;
Reducing undesirable expenses at increasing power of the stations;
Reducing investment in power line and distribution systems;
Reducing of dependence from gas and oil supplies because of reduction in their use and transition to preferred use of coal, ethanol and biogas;
Reducing of hazardous emissions, which cause acid rains and warming;
Increasing of competition of Ukrainian goods in the World market;
Ukraine could be an exporter of fuel cells to the fast growing markets, which so far have no transmission lines, with requirement of 500 GW of new power production by 2010.
 Schrempp J. DaimlerChrysler: Was the merger a mistake? Business Week, 2003, September 29, p. 44-51.
 Alternative Fuel Vehicles. ISATA Magazine, issue 10, June 2000, p.16.
 Karamyan G.G. Oganes Davtjan, Lpatu, Yerevan, 2001, 100 p., in Russian.
 Molten Carbonate Fuel Cells, http://americanhistory.si.edu/csr/fuel cells/
 Baklan V.Yu. This book
 Davtjan O.K. Theory of Fundamental Field, Aiyastan, Yerevan, 1995, 313 p., in Russian.
 Davtjan O.K. The problem of direct transformation of energy of fuel into electricity. Academy of Science of USSR, Moscow, 1947, in Russian.
 Ivaschenko O.V., Vasilev A.D., Peitchev V.G. et al. Fracture mechanisms, and strength of zirconia stabilized partially with yttria. Physical and chemical mechanics of materials, 1992, v.28, N6, p.46-50, in Russian.
 Vasylyev O.D., Akymov G.Ya, Koval O.Yu. Zirconia ceramics and their prospects in Ukraine. Refractories and technical ceramics, 2000, N10, p.2-5, in Russian.
 Vasylyev O.D., Schokin A.R. Ceramic Fuel Cells: Achievements and Perspectives in Ukraine. Electroinform, 2003, N1, p. 24-27, in Ukrainian.
 Vasylyev O.D., Schokin A.R. Ceramic Fuel Cells. In: Energy Saving in Regions. State Committee on Energy Saving, Analytical Issue, Alternative Energetics, Kyiv, 2003, p. 57-61, in Ukrainian.
 Vasylyev O.D., Burdin V.V. Fuel Cells. Electroinform, 2004, N1, p. 10-12, in Ukrainian.
 Vasylyev O.D. Fuel Cells: The Target Program. Electroinform, 2004, N1, p. 46-47, in Ukrainian.
Author: O.D. VASYLYEV
Frantcevych Institute for Problems of Materials Science, National Academy of Science of Ukraine; Zirconia Ukraine Ltd. 3, Krzhyzhanivs’koho Str., Kyiv-142, 03680, Ukraine