Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/383—Hydrogen absorbing alloys
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C22/00—Alloys based on manganese
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C30/00—Alloys containing less than 50% by weight of each constituent
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
  • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
  • H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/32—Hydrogen storage
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S420/00—Alloys or metallic compositions
  • Y10S420/90—Hydrogen storage

Definitions

• This invention relates to alloys in which hydrogen may be stored, more particularly to such alloys or materials which are non-pyrophoric on exposure to ambient atmosphere, and most particularly to such non-pyrophoric alloys which may have a heterogeneous spectrum of hydrogen bonding energies.
• Hydrogen generally considered to be the ultimate fuel, presents numerous potential benefits to be realized as well as numerous difficulties to be overcome. With capacity to serve as a fuel for combustion engines, other processes in which heat energy is derived from combustion and used; as well as a direct source of electrochemical energy in direct conversion processes such as, for example, those used in electrochemical fuel cells, hydrogen presents opportunities for production of energy without the creation of waste products bearing disposal difficulties.
• magnesium-based hydrogen storage alloys are high-temperature alloys as they generate a great deal of heat during hydriding and require a similar amount of heat to reverse the reaction and release hydrogen; their storage capacities are generally beyond about 5% by weight.
• Low temperature alloys generally transition-metal based and often of the AB 2 structure, generate less heat during charging or hydriding, require less heat to release hydrogen, and have storage capacities generally around or below about 2% hydrogen by weight. Such alloys will normally release hydrogen at ambient temperatures simply by opening a valve and on whatever container is used for containment of the storage material, thereby reducing the hydrogen pressure around the storage material or alloy which in turn drives the previous reaction forward.
• the low temperature alloys particularly in light of their easy acceptance of oxygen and rapid formation of oxides, likely will release tremendous amounts of heat upon exposure to ambient atmosphere. Such rapid release of heat yields a material which can easily heat to glowing red almost instantaneously and burst into flames and/or ignite other material nearby whose ignition temperature is at or below the temperature of the glowing metal.
• These alloys or hydrogen storage materials because of their affinity for oxygen are normally simply pyrophoric. Such pyrophoricity means that the materials must be treated with respect and handled with care under non-reactive atmosphere. Even more important, from the standpoint of distribution and enhancement of hydrogen storage capacity, the pyrophoric nature of these materials require special handling (read: more costly) in transportation.
• multi-elemental hydrogen storage materials are atomically engineered and designed into non- pyrophoric hydrogen storage alloys by considering them as a system.
• These multi-elemental alloys can also be made in a non-equilibrium manner so that not only compositional disorder is produced, but also the desired local chemical order is formed.
• This revolutionary breakthrough has been made possible by considering the materials as a system and thereby utilizing chemical modifiers and the principles of disorder and local order, pioneered by Stanford R. Ovshinsky (one of the instant inventors), in such a way as to provide the necessary catalytic local order environments, such as surfaces and at the same time designing bulk characteristics for storage and high rate charge/discharge cycling.
• these principles allow for tailoring of the material by controlling the particle and grain size, topology, surface states, catalytic activity, microstructure, and total interactive environments for storage capacity.
• Such disordered materials are formed of one or more of amorphous, microcrystalline, intermediate range order, or polycrystalline (lacking long range compositional order) wherein the polycrystalline material may include one or more of topological, compositional, translational, and positional modification and disorder, which can be designed into the material.
• the framework of active materials of these disordered materials consist of a host matrix of one or more elements and modifiers incorporated into this host matrix. The modifiers enhance the disorder of the resulting materials and thus create a greater number and spectrum of catalytically active sites and hydrogen storage sites.
• the disordered electrode materials of the '597 patent were formed from lightweight, low cost elements by any number of techniques, which assured formation of primarily non-equilibrium metastable phases resulting in the high energy and power densities and low cost.
• the resulting low cost, high energy density disordered material allowed such Ovonic batteries to be utilized most advantageously as secondary batteries, but also as primary batteries and are used today worldwide under license from the assignee of the subject invention.
• the improved characteristics of the anodes of the '597 patent were accomplished by manipulating the local chemical order and hence the local structural order by the incorporation of selected modifier elements into a host matrix to create a desired disordered material.
• the disordered material had the desired electronic configurations which resulted in a large number of active sites.
• the nature and number of storage sites was designed independently from the catalytically active sites.
• Multiorbital modifiers for example transition elements, provided a greatly increased number of storage sites due to various bonding configurations available, thus resulting in an increase in energy density.
• the technique of modification especially provides non-equilibrium materials having varying degrees of disorder provided unique bonding configurations, orbital overlap and hence a spectrum of bonding sites. Due to the different degrees of orbital overlap and the disordered structure, an insignificant amount of structural rearrangement occurs during charge/discharge cycles or rest periods therebetween resulting in long cycle and shelf life.
• the improved battery of the '597 patent included electrode materials having tailor-made local chemical environments which were designed to yield high electrochemical charging and discharging efficiency and high electrical charge output.
• the manipulation of the local chemical environment of the materials was made possible by utilization of a host matrix which could, in accordance with the '597 patent, be chemically modified with other elements to create a greatly increased density of catalytically active sites for hydrogen dissociation and also of hydrogen storage sites.
• the disordered materials of the '597 patent were designed to have unusual electronic configurations, which resulted from the varying 3-dimensional interactions of constituent atoms and their various orbitals.
• the disorder came from compositional, positional and translational relationships of atoms. Selected elements were utilized to further modify the disorder by their interaction with these orbitals so as to create the desired local chemical environments.
• the internal topology that was generated by these configurations also allowed for selective diffusion of atoms and ions.
• the invention that was described in the '597 patent made these materials ideal for the specified use since one could independently control the type and number of catalytically active and storage sites. All of the aforementioned properties made not only an important quantitative difference, but qualitatively changed the materials so that unique new materials ensued.
• the disorder described in the '597 patent can be of an atomic nature in the form of compositional or configu rational disorder provided throughout the bulk of the material or in numerous regions of the material.
• the disorder also can be introduced into the host matrix by creating microscopic phases within the material which mimic the compositional or configu rational disorder at the atomic level by virtue of the relationship of one phase to another.
• disordered materials can be created by introducing microscopic regions of a different kind or kinds of crystalline phases, or by introducing regions of an amorphous phase or phases, or by introducing regions of an amorphous phase or phases in addition to regions of a crystalline phase or phases.
• the interfaces between these various phases can provide surfaces which are rich in local chemical environments which provide numerous desirable sites for electrochemical hydrogen storage.
• compositional disorder is introduced into the material which can radically alter the material in a planned manner to achieve important improved and unique results, using the Ovshinsky principles of disorder on an atomic or microscopic scale.
• One advantage of the disordered materials of the '597 patent were their resistance to poisoning. Another advantage was their ability to be modified in a substantially continuous range of varying percentages of modifier elements. This ability allows the host matrix to be manipulated by modifiers to tailor-make or engineer hydrogen storage materials with all the desirable characteristics, i.e., high charging/discharging efficiency, high degree of reversibility, high electrical efficiency, long cycle life, high density energy storage, no poisoning and minimal structural change.
• Ovshinsky's atomic engineering principals to provide low temperature hydrogen storage alloys that are non-pyrophoric.
• Upon application of these principles to low temperature alloys have provided a non-pyrophoric hydrogen-storage material. Specifically provided are low-temperature hydrogen storage alloys with acceptably high hydrogen storage capacity, cost-effective composition, reasonably high absorption/desorption hydrogen storage kinetics coupled with non-pyrophoricity.
• This invention relates to alloys in which hydrogen may be stored, more particularly alloys known as "low temperature” hydrogen storage alloys or materials, and specifically to such alloys or materials which are non-pyrophoric on exposure to ambient atmosphere, even after hydride/dehydride cycling.
• the alloy comprises titanium, zirconium, vanadium, chromium, and manganese.
• the alloy may preferably further comprise iron and aluminum and may also contain 1-10 at. % total of at least one element selected from the group consisting of Ba, Co, Cu, Cs, K, Li, Mm, Mo, Na, Nb, Ni, Rb, Ta, Tl, and W (where Mm is misch metal).
• the low temperature hydrogen storage alloy comprises 0.5-10 at. % Zr, 29-35 at. % Ti, 10-15 at. % V, 13-20 at. % Cr, 32-38 at. % Mn, 1.5-3.0 at. % Fe, and 0.05-0.5 at. % Al.
• the alloy remains non-pyrophoric upon exposure to ambient atmosphere even after 400 hydrogen charge/discharge cycles, and preferably even after 1100 hydrogen charge/discharge cycles.
• the alloy has a hydrogen storage capacity of at least 1.5 weight percent, more preferably at least 1.8 weight percent, and most preferably at least 1.9 weight percent.
• Figure 1 is a graphic depiction of the desorption PCT curves of two non- pyrophoric alloys of the instant invention
• Figure 2 is a graphic depiction of the absorption kinetics of one non- pyrophoric alloy of the instant invention at 35, 437, and 1108 hydride/dehydride cycles;
• Figure 3 is a graphic depictions of the desorption PCT curves of the two comparative (pyrophoric) alloys
• Figure 4 is a graphic depiction of the absorption kinetics of comparative alloy OV56 at 40, 177, 351 , 466, and 669 hydride/dehydride cycles.
• the instant invention provides for a low temperature hydrogen storage alloy which is non-pyrophoric upon exposure to ambient atmosphere.
• the alloy particularly is non-pyrophoric even after hydrogen charge/discharge cycling.
• the inventors have created an atomically engineered TiMn 2 type alloy.
• Preferred embodiments of the non-pyrophoric low temperature hydrogen storage alloy comprises titanium, zirconium, vanadium, chromium, and manganese.
• the alloy may further include iron and aluminum.
• Atomic engineering of the instant alloy included adjusting the composition of the alloy to include increased chromium levels beyond that of conventional TiMn 2 alloys. That is, the inventors have found that as the chromium content of the alloy increases, the tendency to be pyrophoric decreases.
• alloy compositions comprise 0.5-10 at. % Zr, 29-35 at. % Ti, 10-15 at. % V, 13-20 at. % Cr, 32-38 at. % Mn, 1.5-3.0 at. % Fe, and 0.05-0.5 at. % Al.
• Specific examples of useful alloys include the compositions Z Ti 33 V 1254 Cr 15 Mn 36 Fe 225 AI ⁇ 21 and Zr 1 5 Ti 325 V 1254 Cr 15 Mn 36 Fe 225 Al 021 .
• particularly preferred embodiments may consist of the basic non-pyrophoric alloy which has been modified to create heterogeneity within the spectrum of hydride bond strengths, with one or more body-centered cubic structure by incorporation of at least one element selected from the group consisting of barium, cesium, potassium, lithium, molybdenum, sodium, niobium, rubidium, tantalum, thallium, and tungsten.
• the alloys of the instant invention remain non-pyrophoric upon exposure to ambient atmosphere even after 400 hydrogen charge/discharge cycles and more preferably remain non-pyrophoric upon exposure to ambient atmosphere even after 1100 hydrogen charge/discharge cycles.
• the alloys have a hydrogen storage capacity of at least 1.5 weight percent, more preferably at least 1.8 weight percent and most preferably at least 1.9 weight percent.
• Inventive Example 1 A first inventive hydrogen storage alloy (designated OV555) having the composition Z Ti 33 V 1254 Cr 15 Mn 36 Fe 225 Al 021 (all atomic subscripts are based upon a total of 100 atoms) was made by melting and casting into an ingot. The alloy was comminuted by crushing followed by successive hydriding and dehydriding cycles. The material was allowed to outgas to evolve and release as much hydrogen as possible. Several grams of the outgassed powder were poured in a cascade through ambient atmosphere from a height of about 75 cm into a metal bucket having open diameter of about 30 cm. The powder warmed considerably and began to glow but did not ignite. The test was repeated with the same results. Inventive Example 2
• a second inventive hydrogen storage alloy (designated OV557) having the composition Zr 1-5 Ti 325 V 1254 Cr 15 Mn 36 Fe 225 Al 021 (all atomic subscripts are based upon a total of 100 atoms) was made by melting and casting into an ingot. The alloy was comminuted by crushing followed by successive hydriding and dehydriding cycles. The material was allowed to outgas to evolve and release as much hydrogen as possible. The material was tested according to the same procedure as was the material in Inventive Example 1. Thus, several grams of the outgassed powder were poured in a cascade through ambient atmosphere from a height of about 75 cm into a metal bucket having open diameter of about 30 cm. The powder did warm considerably and began to glow but did not ignite. The test was repeated with the same results.
• Figure 1 is a graphic depiction of the desorption PCT curves of the two inventive materials OV555 (symbol A) and OV557 (symbol •) at 0°C.
• the two inventive alloys demonstrate an absorption maximum of about 1.9 wt.%.
• the inventive alloys have a sloped plateau pressure that ranges from about 2 to about 10 bar. This sloped plateau pressure is indicative of the heterogeneous spectrum of hydrogen bonding energies that exist in the inventive alloys.
• Figure 2 is a graphic depiction of the absorption kinetics of inventive alloy
• a first comparative hydrogen storage alloy (designated OV56) having the composition Zr 435 Ti 295 V 575 Cr 635 Mn 439 Fe 8 15 Al 20 (all atomic subscripts are based upon a total of 100 atoms) was made by melting and casting into an ingot.
• the alloy was comminuted by crushing followed by successive hydriding and dehydriding cycles. The material was allowed to outgas to evolve and release as much hydrogen as possible.
• Several grams of the outgassed powder were poured in a cascade through ambient atmosphere from a height of about 75 cm into a metal bucket having open diameter of about 30 cm. The powder did warm considerably and began glowing, sparking and igniting during its fall.
• a second comparative hydrogen storage alloy (designated OV539) having the composition Zr 363 Ti 2g 8 V 882 Cr g 85 Mn 395 Fe 5 Al 1 0 Ni 2 Mm 04 (all atomic subscripts are based upon a total of 100 atoms) was made by melting and casting into an ingot. The alloy was comminuted by crushing followed by successive hydriding and dehydriding cycles. The material was allowed to outgas to evolve and release as much hydrogen as possible. Several grams of the outgassed powder were poured in a cascade through ambient atmosphere from a height of about 75 cm into a metal bucket having open diameter of about
• Figure 3 is a graphic depictions of the desorption PCT curves of the two comparative examples, OV56 (symbol •) and OV539 (symbol ⁇ ) at 30°C.
• OV56 symbol •
• OV539 symbol ⁇
• Figure 4 is a graphic depiction of the absorption kinetics of comparative alloy OV56 at 40 (symbol ⁇ ), 177 (symbol ⁇ ), 351 (symbol A), 466 (symbol ), and 669 (symbol ) hydride/dehydride cycles.
• the data was taken at a hydrogen pressure of 300 pounds per square inch and at 0°C.
• the kinetics have remained relatively constant (shape of the curve), but the capacity has decreased somewhat. Again, this decrease in capacity is due to contamination of the alloy by impurities in the hydrogen used for cycling.
• Anotherform of atomic engineering forthese alloys may be accomplished is through vehicle of adjusting various aspects of the TiMn 2 -type alloy.
• the alloy structure may be adjusted by modification of the A to B ratios away from the stoichiometric ratio of 1 :2.

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• 2001
  • 2001-06-04 US US09/873,863 patent/US6517970B2/en not_active Expired - Lifetime
• 2002
  • 2002-06-03 JP JP2003502257A patent/JP3940720B2/ja not_active Expired - Fee Related
  • 2002-06-03 DE DE60217345T patent/DE60217345T2/de not_active Expired - Lifetime
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  • 2002-06-03 WO PCT/US2002/017464 patent/WO2002099149A1/en not_active Ceased
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