Science of Sintering, 34 (2002) 247-259 UDK 62-492.3: 546.11: 52-657 Modern Concepts of Conversion and Storage of Energy by Dispersed Materials Absorption D. Minié* M. V. Susie? ' Physical Chemistry Faculty, University of Belgrade, Studentski Trg 12-16, Belgrade, Serbia, Yugoslavia ? Serbian Academy of Sciences and Arts, Knez-Mihailova 35, Belgrade, Yugoslavia Abstract: Once hydrogen is generated, the question asked: How do we store hydrogen? Hydrogen can be stored in a variely of ways, each with specific advantages and disadvantages. The overall criteria for choosing a storage method should be safety and ease of use. Described in this paper and listed below are different storage methods available today (compressed hydrogen, liquid carrier storage, glass microsphere, chemically stored hydrogen) in addition to some techniques that are stil in the research and development stage: power balls, metal hydride tanks and carbon clusters. Keywords: Hydrogen; Conversion; Storage; Metal hydrides; Carbon nanotubes, Graphite nanotubes. Pesiome: Ip mpowssoscrse soopoxa vosmxacr wonpoc ero akkymyauponanns, Cimectnyer neckomexo cnocoGox cro aRKYMY:INpODAUINA, 2 KOTOpLIX Kaxyorit HMeeT CBO Npenuymectsa 4 negocrarsu. OOuuit xpurepmit nat petGopa cnocoba axxysy:zanam nanexnoe H serkoe upaMencune. B jannott paGore oncassr pazmnuste Yo cnx nop USBECTHBIE CHOCO! AKKYMNINpOBAHNA HONOpONA, C ONIEMHEIM aceKTOM Ha Mero PasbusanoUMecs B HACTOMUICe HpEMS. Kmovesbie cnosa: Bojopor, mpeodpasovanne; axkyMyanposatne; MeTannTecKne PmapHL Veneposuste masnoTpyOKK, rpaipiTonble Hano1pyGK. Cagpmal: Mon nponseogien BopoKNKa NocTasma Ce MuTalbe HeroBOr cKNagMUsTerba. BogoHnk Moxe ga 6yAe CknagMUITeH Ha pasHe HaYHKe, Of KOJAX CBaKM Hua HHS peAHOCTH ann HepoctaraKa. Onwrn KpuTepniym sa nsGop HaunHa ckKnagnuTena Tpeba Aa 6yge Ha npBOM MecTy naka 4 6es6eqHa npMMeHa. Y OBOM Papy ONMCAHA cy Pash NOCTYNYM JaHac ‘Aoctynkn 3a cKNagnUTere BOAOKHKa, Ca NOGeGHHM HarnaCKOM Ha OHe KojM ce caga pasanjaly. Krysne pew: Bogornk; KoHeepsija; cknagmulrese; MeTankH xXHApHAM; yrreenmne HaHoyesn; (pacbuTHe HaHOYyeEn. * Corresponding author: dminic@ffh.bg.ac.yu248 1. Introduction ‘The largest amount of sun’s energy and other renewable forms of energy are available only in certain weather conditions, and require storage for later use. The most important technologies used for storage of this type of energy use modern batteries (lithium-ion, nickel- metal hydride, air metal hydride, ete.), hydrogen storage and fuel cells. Hydrogen fuel is, because of its great availability (also its regeneration) in nature and the fact that it releases a great amount of energy while producing no environmental pollution, considered by many to be the “energy carrier” of the future. It is called an energy carrier and not an energy source because it takes a primary energy source to produce it. The energy is released on demand by combustion or by electrochemical conversion directly to electricity in the fuel cell. The product of the process is in all cases water and therefore hydrogen is the ultimate “clean fuel”. Such fuel might solve the world’s growing need for thermal and electrical power along with energy transportation. This is why today hydrogen production and storage are primary research interests in the search for new energy sources Hydrogen is the most abundant element in nature (the universe consists of 93% of hydrogen), and it is commonly found in the shape of its most common compounds from which it is extracted through various techniques. For hydrogen production, where it is bound ‘ous photobiological, chemical and electro-chemical techniques exist. All of the previous techniques require certain consumption of energy. One of the well-known techniques for hydrogen production is photolysis where energy of the sun is used to split water molecules into hydrogen and oxygen molecules, with other elements in nature, va 2, Storage of energy Once produced hydrogen can be stored using various techniques which have a number of advantages but also many disadvantages. The prime criterion for choosing which storage technique to use is to provide a safe and easy way to store hydrogen. These techniques deal with physical means of storing energy, where hydrogen might be compressed or transferred to liquid state, as well as chemical storage and gas-solid interaction (absorption) (1-5}, ‘Among all these techniques, today, the most practical and most economical techniques are compression of hydrogen in its gas state, extraction and maintenance of liquid hydrogen and utilization of chemical compounds for hydrogen storage, The newest and most promising hydrogen storage research is focused on creation of new dispersed materials (power balls, hydrides and carbon clusters), which are suitable for hydrogen absorption at room temperature and normal pressure [11-34] 2.1. Compression of hydrogen Nowadays, commercially available hydrogen in its gas state can be compressed at room temperature and pressure of 24.8 MPa into glass fiber strengthened aluminum cylinders with density 12 kg/m’ and gravimetric density of 2 wt.%. Polymeric cylinders, strengthened with carbon fibers, provide higher density (15 kg/m’, 5 wt.%), but it is much lower than the density required by vehicles with fuel cells (62 kg/m’ and 6.5 wt.%). Light composite cylinders secure hydrogen under gravimetric density of 12 wt.% and pressure 33.8 MPa, when249 they are completely filled [6-7]. Compared to petrol, thus compressed hydrogen volume is larger and, consequently, has lower energy density. More precisely, the energy density of petrol equivalent is around 3000 times higher than the one related to compressed hydrogen. ‘On the other hand, compression requires energy consumption to a certain degree, so that 10 % of complete stored energy is consumed, by compression of hydrogen. These 225 liters containers, and larger ones, are used for motoring cars and buses with fuel cells, respectively (Los Angeles, Chicago ~ USA). Hydrogen can be compressed in containers at pressure up to 41.22 MPa, while every new 28 liters of compressed gas, added in the same container, increase the pressure for additional 0.101 MPa. Because of extremely high pressure, these containers require permanent control and occasional testing. 2.2. Liquid hydrogen Liquid hydrogen can exist only at extremely low temperatures (20 K or ~253°C) and such a state is hard to reach and maintain [7-9]. Density of thus stored hydrogen is 845 times higher, compared to the one of gaseous hydrogen at normal conditions. It has a low mass (one liter of liquid hydrogen has 0.07 kg in weight while the same volume of petrol has 0.84 kg in weight), but 4 times lower energy density compared to petrol (4 liters of hydrogen are energetically equivalent to a liter of petrol), and has a 3 times higher energy value per weight unit. Conversion of hydrogen into its liquid state by cooling and compressing requires 30 % of stored energy. On the other hand, keeping hydrogen liquid apart from temperature maintaining needs application of special highly isolated containers equipped for liquid hydrogen storage under pressure. Even under these conditions, 1-2 % of stored hydrogen evaporates every day, and it has to be safely stored. Considering all this, such storage of hydrogen as a method is expensive and unsuitable for common application. However, due to its low weight, liquid hydrogen is the fuel of choice in spacecrafts, where conditions for attaining low temperature are much more suitable than the ones on Earth. The purpose of research in this area is construction of light containers made of composite materials, strengthened in order to keep liquid hydrogen and improvement of preparation of hydrogen in this state. 2.3. Cryogenic activated carbon Carbon activated by cooling (cryogenic carbon) can be used for hydrogen storage, too [1-2, 10}. This technique has developed rapidly. The best results were achieved with carbon cooled at 77 K (-196°C). Thus stored hydrogen density approaches the density of liquid hydrogen, 2.4. Chemically stored hydrogen [As the most abundant element in the universe, hydrogen appears in the form of its compounds. These compounds can be used for hydrogen production, and some, for its storage [11]. A stable hydrogen compound, produced in the first stage, can release hydrogen in a chemical reaction, which can be collected and used for energy production in fuel cells. Some of these reactions include ammonia cracking, methanol cracking, electrolysis of water, etc. In250 this case, there is no need to store released hydrogen, because it is extracted when needed. For example, methanol is introduced directly into the cell. Methanol and water convey into a gas, state and produce hydrogen, CO, CO; at 280°C. After catalytic oxidation, in order to remove CO (there is a quantity of 10-20 ppm of CO), the gas transfers directly onto the positive terminal of the fuel cell. Hydrogen can be stored in the form of fossil fuel (petrol, gas, etc.), which are widely used hydrogen sources. In a technique, known as Storage of liquid carrier, fossil fuel undergoes the process of “reforming”. Such hydrogen can hold additional CO that originates from fossil fuel and may pollute certain types of fuel cells. Therefore, produced hydrogen has to be purified in order to remove excess CO. ‘A more current technology of hydrogen chemical storage, which doesn't require energy for releasing hydrogen, is the so called Power ball technology. This new technology refers to its compounds, which in an exothermic reaction, reacts with water to extract, hydrogen. Alkaline metal hydrides (Na, Li or K) are most suitable for this purpose. A hydride pellet, as needed, reacts with water to release hydrogen. This hydrogen is used as fuel and forms a suitable hydroxide solution that can be recycled. Power balls available today include balls or pellets with water resistant coating (polyethylene). Polyethylene coating prevents the reaction of sodium hydride with water and uncontrolled loss of energy. Thus protected balls ‘can be stored directly in water and as needed, after breaking of the coating, a sodium hydride ball (one inch in diameter) completely reacts with water within 10 seconds, releasing hydrogen, which bums with oxygen. Both of these reactions are exothermic, so the hydrogen production doesn't require energy: NaH + H,0 ~ NaOH + H; (pellet reaction) H, +050) -> H,0 (fuel combustion reaction) NaH + 0.50; NaOH (whole reaction) The reaction scheme shows that 12 grams of NaH yield 1 gram of hydrogen. In a stored form, power balls (pellets) consume only 65 % of the total volume of its container. Pellet coats and spaces between them, filled with water, fill the rest of the volume. One liter of power balls (NaH density is 1.396 g/cm’) produces 76 grams of hydrogen or 845.45 liters (measured at sea level and room temperature), It has to be emphasized, for comparison, that one-lter of liquid hydrogen and methanol yield 778 and 1001 liters of hydrogen in a gas state, respectively (measured at sea level and room temperature). According to the same reaction cheme 1 liter 0 f power balls produce 38,02 moles or 1520.29 grams of NaOH with a density of 2.130 g/cm’ and volume of 12.7 liters. Thus produced sodium hydroxide can be stored in a container, which previously held power balls and recycled later, for sodium hydride production, using electric or solar energy. 2.5. Glass micro spheres ‘These hollow glass balls, 25-500 jum in diameter with 1 um thick walls, can be used for safe hydrogen storage [12]. Empty glass balls are heated to a temperature range 200-400°C, making its walls more permeable. Balls are'filled with hydrogen by putting it into gaseous hydrogen under pressure. Then, balls are cooled retaining hydrogen. The balls release the contained hydrogen with repeated heating. Such balls are inert, resistant to contamination and require small amount of heat to release hydrogen.251 2.6. Dispersed systems A new concept of hydrogen storage is aiming on the use of dispersed systems, icc. metal hydrides, polymer-dispersed metal hydrides and carbon clusters. It is known that many dispersed systems, metals and its alloys, absorb hydrogen at relatively low pressures. Because of this property, they are used as hydride containers for the storage of hydrogen. More precisely, metals have a unique ability to absorb hydrogen and release it later, both at room or higher temperatures. The whole amount of hydrogen absorbed in this way, is usually 1-2 % of the whole weight of hydride, even though some hydrides absorb 5-7 % at higher temperatures (250°C) [9] 2.6.1. Metal hydrides Metal hydrides are solid compounds of hydrogen and metal or metal alloy [13-24] Certain alloys absorb easily large amounts of *® e gaseous hydrogen reversibly at pressure around * e ambient pressure as shown in Fig. 1 H,Gas Solid Metal Metal-hydrogen systems consist of a metal phase, gas phase (hydrogen in gas state) and Fig. 1 A simplified model of hydrogen-metal interphase surface, Fig. 1. Hy molecules are interaction, adsorbed at the interphase surface and divided to give atoms. The yielded hydrogen atoms might be absorbed or dissolved in a metal phase, releasing a large amount of heat. By suitable tailoring of the metal alloy it is possible to obtain almost any desired bond strength resulting in the desired equilibrium pressure. This is the storage pressure at which hydrogen is either absorbed or desorbed. Thus yielded and disordered solution of hydrogen in a metal phase is known as, a-hydride phase. In a metal phase, hydrogen atoms might consolidate and form specific configuration with metal atoms, specific for the type of metal, known as f-hydride phase. The way nucleation develops, its location and f- phase growth, depend on characteristics of the metal. The reaction of hydrogen with the metal can be presented like this: M + x/2H, © MH, + heat The reaction is reversible - it reaches equilibrium, and then changes direction with the change of conditions. According to the right side of the reaction, heat is released, when hydride is produced and it is consumed when hydrogen escapes from metal hydride. The amount of reaction enthalpy is the strength indicator of the metal-hydrogen bond in metal hydride. I. Thermodynamic aspect of hydride forming The best way to describe equilibrium between metal and hydrogen is by a pressure- composition isotherm, also called a PCT curve. An ideal isotherm, three temperatures PCT curves is, shown in Fig. 2a.[ne | fn 8 and 6 os Coen, ” ® 2 Three isotherm PCT curves (a); change of equilibrium pressure with temperature (b). ‘The slope on the left side of PCT curves indicates that with the presence of an achydride phase, big change of hydrogen pressure causes a slight change of dissolved hydrogen concentration in the metal phase. Meanwhile, when the B-hydride phase starts to form, more exactly, when both hydride phases are present, a slight change of hydrogen pressure causes a big change of absorbed hydrogen concentrations in the metal phase. Furthermore, when the material saturates with the f-hydride phase (right side of PCT curves) than again, a big change of hydrogen pressure causes a slight change of absorbed concentration in the metal phase. A plato, which indicates the existence of both phases in equilibrium, at the same time, is the so called equilibrium pressure plato, and it is a characteristic of that material. Temperature growth also increases the content of hydrogen in the metal phase. \Van't Hoff's equation describes the proportion between pressure and temperature: Ln p =AHRT ~ ASIR, where p is the equilibrium pressure of hydrogen, AH and AS are enthalpy and entropy of the ly, R is the universal gas constant and T is the reaction of hydrogen absorption, respect absolute temperature. Van't Hoffs equation shows that the temperature raise increases the pressure of hydrogen, so it is possible to absorb hydrogen at low pressure and temperature and then to heat the hydride to incite desorption of hydrogen at much higher pressure. By measuring the equilibrium pressure at various temperatures (Fig. 2b) utilization of this equation enables determination of the enthalpy and entropy of hydrogen absorption in the metal phase. II. Application of metal hydrides for hydrogen storage The ability of metal and its alloys to absorb great amounts of hydrogen at relatively low pressures made possible their utilization for hydrogen storage (Tab. 1). The most exploited systems for this purpose are MgHs, FeTiHz, LaNiHs, MgoNiHs [4-5]. Hydrogen atoms intensely react with electron gas of metal atoms (they are being absorbed), releasing a great amount of heat. A reduction of rotational degrees of freedom, caused by absorption, brings about a decrease of bonded hydrogen atom diameter, so it is possible to draw them near each other, much closer, than in liquid hydrogen. However, the metal phase weight is still to a great extent higher than that of stored hydrogen. Consequently, metal hydrides are hydrogen density in metal hydrides is much higher than the one for gaseous or liquid hydrogen. unsuitable for economical application in transport means. StilHydrogen, produced in this way, is of a great purity, and the life of such a hydride container depends on the presence of impurities. The alloy acts like a sponge, soaking up water and absorbs hydrogen as well as the impurities present. After the release of hydrogen, these impurities permanently bind to the metal and decrease its ability for further absorption of hydrogen. In order to obtain alloys suitable for different applications, the. properties of hydrides ‘can be controlled by changing the composition and microscopic structure or by treating the surface, e.g., substituting or adding other metal elements. Particular progress in this area is in the application of amorphous and disordered metal hydrides with required hydrogen storage qualities. The presence of platinum and palladium in amount less than 0.1 % has a favorable influence on this process as presented in the work of professor Susié et al. In this case, comparing to the disperse pure substance, Pt and Pd are very active catalysts and activators of hydrogen reactivity so that absorption of Hp carries on much faster and at considerably lower temperatures, due to the known hydrogen spillover effect (HSE) into the crystal lattice. During the HSE at the surface of metal particles (Pt, Pd), which are dispersed at absorbent, easily carries on dissociation of hydrogen molecules according to reaction H + 2H.Thus produced, very reactive hydrogen is spilled into the absorbent crystal lattice and easily yields hydride, where further dissolving take place. 2.6.2. Nanocrystalline metal hydrides This a new class of hydrogen absorbing alloys [24]. These are polycrystals with a typical grain size < 20 nm. Their advantages are to maintain their integrity upon cycling and to show enhanced absorption/desorption kinetics. Examples of these materials, which can be by mechanical alloying, are FeTi and MgsTi. A major drawback is the reduced maximum capacity. Although, the percentage of absorbed gas is sometimes low, in spite of the high price of these materials and their big weight, hydrides obtain safe hydrogen storage and its delivery at constant pressure. ‘Metal hydrides, dispersed in a polymetric matrix (PDMH) are the newest approach in this field [26-28]. The goal is to advantageously combine the volumetric storage capacity of metal hydrides, with the low density of polymeric materials, in an effort to improve the synthesized easil gravimetric storage capacity by factors of 2-5 relative to non-dispersed metal hydrides. In addition, it is conceivable that dehydrating temperatures may be reduced, potentially enabling ‘automotive waste heat to effectively dissociate the hydride. Dispersion of the metal hydride in 1a polymer support phase may also increase the stability of the metal hydride, possible through reduction of hydride decrepitating. It was shown that relatively low gravimet slightly enhanced by incorporating a low-density polymer that can both interact with the hydride on a molecular level, and store additional hydrogen within the polymer structure, Fig. 3 ¢ capacity of metal hydrides could be ‘The exact role that a polymer plays in modifying the hydrogen storage capacity of a metal hydride is unknown at this time. It is plausible that a polymer structure could interact, with molecular hydrogen. Given that each polymer contains a high concentration of hydrogen covalently bonded to the polymer structure, it is conceivable that hydrogen species could254 interact on a molecular level. For example, depending on the charge of hydrogen species, a combination of covalent, ionic, metallic, H-bonding and Van der Waals interactions could exist within and polymer chains and/or with the metal hydride. Free radicals present within the polymer structure could further participate in hydrogen movement through the polymer network. Although the exact location of the free radical sites has yet to be determined, they can be represented as dangling bonds, As a hydrogen molecule diffuses near a dangling bond, it can dissociate into two hydrogen atoms, which can further interact with the polymer free radical to form a covalent bond, or diffuse into the metal hydride lattice. ‘mpemet 9h S oa 4 Ne. ain Ee a. — emporture. 1% Fig. 3 Hydrogen released from various PDMH. To date, there is little experimental evidence to support the notation that polyme: alone provide significant hydrogen storage capacity, Fig. 3. Investigations continue to examine the inter-relationship between the dispersed metal hydride and the polymer support phase, and the resulting hydrogen storage behavior of the composite. 2.6.3. Carbon clusters This is a new approach in the storage of hydrogen (29-34). The phase diagram of carbon, showed at Fig. 4, illustrates phase transitions between known forms of carbon (graphite and diamond) and it is of a great historical importance, related to the first production of diamond from graphite by synthesis in 1960. Among stable forms of carbon, hexagonal graphite and cubic diamond, hexagonal diamond, hexagonal carbines and liquid carbon forms, exist at higher temperatures and pressures. Recent attention was paid to small carbon clusters, fullerene (ball shaped, consists of 12 pentagon and 20 hexagon rings with 60 atoms in total, Fig, 5a) and nanotubes (cylinders of hexagonal graphite rings that from both ends, capped with half fullerene at each end, Fig. 5b; S. Lijima 1991) of very stable structures [33] ‘Additional system energy decreases with creation of these structures caused by the presence of side graphite atoms with an unutilized binding potential. These forms of carbon have many unique characteristics, great mechanical strength, high electric conductivity, great specific surface, great ability for gas absorption and unique capillary properties. They have a complicated electronic structure, and depending on their chirality, they may have metal or semiconductor properties.255 Fig. 4 Phase transitions of various forms of carbon; A: commercial catalytic production of diamond from graphite by synthesis, B: rapid synthesis of diamond from graphite in a solid phase, C: rapid transformation from diamond to graphite, D: synthesis of hexagonal diamond from hexagonal graphite, E: synthesis of hexagonal diamond by compression of graphite, F: synthesis of cubic diamond by compression of graphite, B, F, G: synthesis of cubic diamond from graphite or hexagonal diamond, H, I, J: compression of graphite at high pressure to have diamond like properties. Fig. S Structure of stable forms of carbon clusters: (a) fullerene Co; (b) carbon nanotube 1. Carbon nanotubes Carbon nanotubes (visible under a microscope) are small light cylinders of a graphite structure, a few molecules in diameter (usually 2 nm) that store hydrogen in microscopic pores on the tubes and inside the structure, in a similar way to hydrides. According to literature, carbon nanotubes can store 4.2 to 65 mass% of hydrogen, depending on the purity and presence of a small quantity of some metal components [29-34]. On the other side, for car industry application, it is enough to be thus stored 6.5 % of hydrogen. This big quantity of hydrogen, thus safely stored, presents the main advantage of this approach and at the same time, the reason why, the development of these materials of a great capacity for hydrogen or some hydrocarbon storage is the latest research topic. The most recent research, in this line of work, is pointed to the production of centered clusters of carbon nanotubes, called carbon nanofibers (usually 5-100 nm in diameter). There are two kinds of nanotubes available today: single atom wall nanotubes (SWNTs) and many atom wall nanotubes (MWNTs). Connected to SWNTs, there is distribution of tube diameter and geometry. Three basic conformations are showed in Fig. 6 (armchair, zigzag and chiral single wall carbon nanotubes). Metal properties are provided by first of these three and with 1/3 of the other two conformations.256 Fig. 6 Schematic models for (a) armchair, (b) zigzag and (c) chiral single-wall carbon nanotubes, Three methods are used for the preparation of carbon nanotubes. The first method includes application of an arc light on a carbon electrode impregnated with metal in order to transit into a gaseous state. The second method uses a laser to transit the carbon target treated with metal (Ni, Co, Fe) into vapor. The third method is known as catalytic chemical vapor deposition (CVD). It is the most suitable method, because it doesn't require a high temperature. Heated metal decomposes hydrocarbon gas (methane, ethylene, acetylene) to carbon and hydrogen. Hydrogen extracts in a vapor form, while carbon draws out in nanotubes, I. Graphite nanofibers Graphite nanofibers (GNF) are new materials in this area with a different morphology that is produced from the dissociation of carbon-containing gases over selected metal surfaces. The solid consists of very small graphite platelets, 3-50 nm in width, which are stacked in a perfectly arranged conformation. These materials are capable of sorbing and retaining in excess 20 liters of hydrogen per gram of carbon when the nanofibers are exposed to gas at pressures of 11.35 MPa at 298 K, a value that is over an order of magnitude higher than the one found with conventional hydrogen storage systems. It is probable that the presence of delocalized x-electrons on the graphite layers is a major contributory factor to the enhancement of the hydrogen absorption observed in the presented system, IIL. Application of carbon clusters for hydrogen storage Pores, the size of a molecule, can absorb big amounts of gas thanks to their great attracting potential (presence of three electrons) [31]. Henée, 6.2 liters of hydrogen per gram of carbon can be absorbed, covering the surface with a single layer of hydrogen molecules. Considerably bigger quantities of hydrogen can be stored, condensing more hydrogen molecule layers between graphite layers of nanofibres. According to measurements, the distance between graphite layers is 0.34 jum, while the hydrogen molecule diameter is 0.26 um. Hydrogen loses its energy (rotational), being absorbed on carbon (heavy interaction with electrons from a graphite structure), which leads to a decrease of its effective diameter to 0.064 um. In this way, 5 hydrogen layers can be packed between graphite layers. Nanofibres are rinsed out of catalytic impurities with acid for introduction of hydrogen into them and257 then heated to 900°C in vacuum to remove absorbed gases. Afterwards, hydrogen is introduced at a pressure of 11.35 atm during 4 to 24 hours. A comparison of results of different hydrogen storage technologies is shown in Fig. 6 with signification reference to applications in cars with fuel cells. Recent tendencies in this area introduce a modification of graphite nanotubes or nanofibres, replacing carbon atoms with other atoms (boron, nitrogen, alkaline metal), which can change their electric properties. In this way, it is possible to achieve densities of absorbed hydrogen of up to 67 mass%, as shown in Tab. I Tab. I Gravimetric density, temperature and pressure of various forms of stored hydrogen [3-24], [Material Hw.) | Tc | Popa ‘SWNT (low purity) 5-10 133 0.040 SWNT (high purity) 8.25 80 718 SWNT (50 % purity) 42 300 10-12 ub 11.26 298 11.35 GNEs (herringbone) 67.55 298 11.35 | GNEs (platelet) 53.68 298 11.35 GNFs (herringbone) o4 208-773 | 0.101, | 20.0 473-673 | _ 0.101 K-GNFs 140 <313 0.101 Graphite 452 298 11.35 | Li-graphite 14.0 473-673 | 0.101 | K-graphite 5.0 <313 0.101 | Graphite + 0.01 % Pd 44 436 0.101 Charcoal + 0.005 % Pd 31 430 0.101 | Mg + 1% Pa 7.66 552 0.101 Co+0.03 % Pd 5.85 463 0.180 3.98 16 0.101 3.60 528 0.101 [i 1.87 316 0.101 | 1.89 3263 0.101 I 15 2263 11.35 Ti(Fep2Mny ) 1.90 280 0.101 Ti(FeosMno2) 1.30 346 0.101 LaNic 149 295 0.101 LaNigAlos 144 318 0.101 MnNNiy Allos 3.33 298 0.101 LaNicHe + 0.03 % Pd 88 450 0.101 LaNigHs + 0.01 % Pa 4 420 0.101 PDMH + 5 % Ti 036 680 0.101 Ta + 0.004 % Pd 9 480 0.101 Crigadsorption 5 77 20 Isooctane/benzene 173 3233 ou (SWNTs = Single wall carbon nanotubes; GNFs = Graphite nanofibers)258 # ¢ Gorm © sok 2 Stopes 2 Stone : ‘tue g Sane = oe § q ee 5 a o 2 4 6 8 © 12 Gravimetric anergy density (wt%) Fig. 7 Installed density of energy for different technologies of hydrogen storage. Reference 1. J. Nitsch, W. Peshka, W. Schnumberger, M. Fischer and H. Eirchert in “Hydrogen as an Energy Carrier”, eds. C. Winter and J. Nitsch, Springer-Verlag, Berlin, 1988 2. $. Hynek, W. Fuller and Bentley, J. Int, Hydrogen Energy, 22 (1997) 601 MV, Susi¢ J. Int. Hydrogen Energy, 22 (1997) 585. 4. C. G. Carter and L. F, Carter, in “Metal-Hydrogen Systems”, ed. N.T. Veziroglu, Pergamon, Oxford, 1981 5. H. Buchner, P, Pelloux-Gervais, M. Muller, F. Grafwallner and P. Luger, in “Hydrogen and Other Alternative Fuels for Air and Ground Transportation”, ed. W.H. Pohl, Wiley, Chichester, UG, 1995. 6. G.J. Hansel, W.G. Matern, N.R. Miller, J. Int, Hydrogen Energy, 18 (1993) 783. 7. BJ. Taylor, J. Int. Hydrogen Energy, 11 (1985) 5. 8. JF. Edsekuty, F.W. Stewart, Safety in the handling of Cryogenic Fluids, The Infernational Cryogenics Monograph Series, Plenum Press, New York, 1996. 9. W. Peschika, Liquid Hydrogen: Fuel of the Future, Springer-Verlag, Wien, New York 1992. 10. R. Chahine, T.K. Bose, Proc. 11" World Hydrogen Energy Conf., Stuttgart, FRG, 1996. 11. M. Epstein, 3"! JAERI Symp. Orai, 1996, Proc. JAERI Conf. 96-010, Japan Atomic Energy Research Institute, 1996, p. 228. 12. EF, Lynch, Int. Symp., Tokyo, NEDO, 1995, p. 99. 13. R. Schulz, S. Boily, Proc. 7" Canadian Hydrogen Workshop, Quebec City, 1995. 14. Y. Osumi, Int. Sympo. Tokyo, NEDO, 1995, p. 131 15. GS. Podkolzin, MR. Watwe, Q. Yan, J.J. Pablo, A.J. Dumestic, J. Phys. Chem. B, 105 (36) (2001) 8550. 16. C.J. Groen, J. Perez-Ramirez, A.A.L. Peffer, Studies in Surfaces Science and Catalysis, 135 (2001) 2862. 17. L. Liwu, J. Weishen, J. Jifei, X. Zhusheng, T. Zhang, F. Yining, K. Yuan, Sh. Jianyi, Science in China, Series B: Chemistry, 42 (6) (1999) 571.259 18. 19. 20. 2 22, 23. 24. 26. 21. 28. 29. 30. S.J. Bradley, W. Busser, Catalysis Letters, 63 (3,4) (1999) 127. Y. Sakka, H. Okuyama, T. Uchikoshi, S. Ohno, Transaction of the Materials Research Society of Japan, 25 (1) (2000) 43. D. Jing-Fa, Current Topics in Catalysis, 2 (1999) 1 C.A. Dillon, M.K. Jones, A.T. Bekkedahl, C.H. Kiang, D.S. Bethune and J.M. Heben, Nature, 386 (1997) 377. DM. MLV. Susié, in “Hydrides as hydrogen accumulators”, Serbian Academy of Science and Arts, Monographs, Vol. DCXLIV, No. 2, Ed. S. Ribnikar, 1999. (in Serbian) MLV. Susié, J. Serb. Chem. Soc., 62 (12) (1997) 1183. MLV. Su8ié, J. Serb, Chem, Soc., 62 (8) (1997) 631. A. Zaluska, L. Zaluski, J.0. Stré-Olsen , J. of Alloys and Compounds, 288 (1999) 217. DT. Jarvi, Hydrogen Storage in Polymer Dispersed Metal Hydrides, UTRC Proposal P.300.0024 (1999), S.R. Wayde, Proceedings of the 2001 DOE Hydrogen Program Review, 2001. AR. Meinzer, US. Patent 5360461, Polymeric Storage Bed for Hydrogen. Y. Ye, C.C. Ahn, C. Withman, B. Fultz, J. Liu, G. A. Rinzler, D. Colbert, A.K. Smith and RE. Smalley, Applied Physics Letters, 74 (1999) 2307. C. Liu, Y.Y. Fan, M. Liu, TH. Cong, M.H. Cheng and S.M. Dresselhaus, Science, 286 (1999) 1127, . A. Chambers, C. Park, K.T.R. Baker and M.N. Rodrigez, J. Phys. Chem. B, 102 (1998) 4253. P. Chen, X. Wu, J. Lin and L.K. Tan, Science, 285 (1999) 91. S. Iijima, Nature, 354 (1991) 56. J. Jagiello, JT. Bandosz, K. Putyera, AJ. Schwarz, J. Chem. Soc. Faraday Trans., 91 (1995) 2929.