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Publication numberUS3922872 A
Publication typeGrant
Publication dateDec 2, 1975
Filing dateFeb 4, 1975
Priority dateFeb 4, 1975
Publication numberUS 3922872 A, US 3922872A, US-A-3922872, US3922872 A, US3922872A
InventorsJames J Reilly, Jr Richard H Wiswall
Original AssigneeUs Energy
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Iron titanium manganase alloy hydrogen storage
US 3922872 A
Abstract
A three component alloy capable of reversible sorption of hydrogen having the chemical formula TiFe1-x Mnx where x is in the range of about 0.02 to 0.5 and the method of storing hydrogen using said alloy.
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Description  (OCR text may contain errors)

United States Patent Reilly et al.

Dec. 2, 1975 IRON TITANIUM MANGANASE ALLOY HYDROGEN STORAGE Inventors: James J. Reilly, Bellport; Richard H.

Wiswall, ,Ir., Brookhaven, both of N.Y.

Assignee: The United States of America as represented by the United States Energy Research and Development Administration, Washington, DC.

Filed: Feb. 4, 1975 Appl. No.: 547,073

US. Cl. 62/48; 75/134 F; 75/l75.5;

252/471; 423/248 Int. Cl. F17C 11/00 Field of Search 62/48; 75/1755, 134 F;

Primary Examirter-Will1am F. ODea Assistant ExaminerRonald C. Capossela Attorney, Agent, or Firm-Dean E. Carlson; Leonard Belkin [57] ABSTRACT A three component alloy capable of reversible sorption of hydrogen having the chemical formula TiFe, Mn, where x is in the range of about 0.02 to 0.5 and the method of storing hydrogen using said alloy.

4 Claims, 2 Drawing Figures lllllll lllllll N I e 3 Lu 10: I D (D m uJ Q: CL

z Q 6 1.0: o I m 2 Q OJ 1 l l l ATOM RATIO, H/M

IRON TITANIUM MANGANASE ALLOY HYDROGEN STORAGE BACKGROUND OF THE INVENTION The invention described herein was made in the course of, or under a contract with the US Atomic Energy Commission.

Hydrogen is a potential fuel for various types of power sources, such as fuel cells, internal combustion 1O engines, gas turbines, etc. It has two great advantages over fossil fuels, it is essentially nonpolluting and it can be produced using several all but inexhaustible energy sources, i.e., solar, nuclear and geothermal. However, a major problem is the difficulty encountered in its storage and bulk transport. Conventional storage methods, i.e., compression and liquefaction, do not appear to be practical in this context.

A possible solution to the problem lies in the use of a metal hydride as a hydrogen storage medium. Several hydrides are of interest but the material most near to practical application is iron titanium hydride, which can be synthesized through the direct union of hydrogen with the intermetallic compound, FeTi.

Our US. Pat. Nos. 3,508,414 and 3,516,263 disclose methods and apparatus for utilizing iron-titanium alloys to store hydrogen by the formation of hydrides.

One difficulty which has been discovered in the use of iron-titanium alloys for hydrogen storage is the effect of the presence of oxygen in the alloys in small amounts. For example, it has been discovered that the presence of oxygen in the amount of 7000 ppm in commercially available iron-titanium reduced substantially the maximum hydrogen that could be stored and the equilibrium dissociation pressure was increased. This had the effect of increasing the costs involved in storing hydrogen by the use of these alloys.

SUMMARY OF THE INVENTION It has been discovered that the addition of manga nese to the intermetallic alloy FeTi in certain specific amounts not only increases the amount of H which can be stored and at a lower pressure but also has the effect of compensating to a significant extent for the presence of oxygen, permitting significant increases in the amounts of hydrogen which can be stored under more convenient and economical pressures.

In accordance with a preferred embodiment of this invention there is provided a three component alloy capable of reversible sorption of hydrogen having the chemical formula TiFe Mn where x is in the range of about 0.02 to 0.5.

There is also provided, in accordance with another preferred embodiment of this invention, a method of storing hydrogen comprising contacting gaseous hydrogen with a solid alloy of TiFe Mn, where x is in the range of about 0.02 to 0.5.

It is thus a principal object of this invention to provide an improved alloy for the chemical storage of hydrogen.

Another purpose is to provide an improved method for the storage of hydrogen.

Other objects and advantages of this invention will hereinafter become obvious from the following description of preferred embodiments of this invention.

BRIEF DESCRIPTION OF THE DRAWING FIGS. 1 and 2 show curves illustrating the H storage characteristics of alloys incorporating the principles of this invention and comparing them with similar alloys not incorporating this invention.

DESCRIPTION OF THE BACKGROUND EMBODIMENTS An alloy in accordance with this invention may be prepared by melting granules or small ingots of Fe, Ti, and Mn in an are or induction furnace within an inert atmosphere followed by cooling.

The cooled alloy, in order to be utilized for the storage of hydrogen is comminuted or granulated and then activated by outgassing at high temperature (300 C) and exposing to H for a short time followed by outgassing again and cooling under hydrogen with about 1 atmosphere pressure.

In order to form the hydride the activated alloy is exposed to H at a pressure usually 10 atmospheres above dissociation pressure at that temperature, due to hysteresis type effects. The hydriding pressure should for best results be at least twice the dissociation pressure because of the already mentioned hysteresis effect.

EXAMPLES An alloy was prepared with the composition (A) of FeTi and the dissociation pressure-composition isotherms for this alloy are shown in FIG. 1. The H dissociation pressure of this alloy can be seen from the curve at 40 C to be at least 7.2 atmospheres and reaches 25 atmospheres at the maximum H concentration. A similar alloy (B) was prepared in which some of the iron was displaced by Mn and had the formula TiFe Mn The dissociation pressures for this alloy at the same temperature, as shown in FIG. 1, range from 0.42 to 9 atmospheres for the same amount of stored H as in alloy (A). In the drawing, the atom ratio, H/M is defined as the ratio of atoms of hydrogen to total atoms of metal.

It was found that for other temperature conditions the presence of Mn displacing some of the iron additionally made it possible to increase the amount of H which could be stored as well as reducing the dissociation pressure. Curves C in FIG. 2 shows isotherms for a FeTi alloy at 55 and C'while curve D shows the isotherm at 61 C for the composition TiFe Mn Not only does alloy D have a lower dissociation pressure but in addition H storage capacity was increased by about 10 percent by weight. This is shown by the upper limits of the curve.

What is claimed is:

1. A three component alloy capable of reversible sorption of hydrogen having the chemical formula TiFe Mn, where x is in the range of about 0.02 to 0.5.

2. The method of storing hydrogen comprising contacting a solid alloy of TiFe Mn, where x is in the range of about 0.02 to 0.5 with gaseous H at a pressure above the dissociation pressure of the hydride.

3. The method of claim 2 in which the pressure of H during contacting is at least twice the dissociation pressure of the hydride for the temperature during contactmg.

4. The method of claim 3 in which the pressure of H during contacting is about ten times the dissociation pressure of the hydride for the temperature during contacting.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2798806 *Aug 19, 1952Jul 9, 1957Rem Cru Titanium IncTitanium alloy
US3508414 *Mar 5, 1968Apr 28, 1970Atomic Energy CommissionMethod of storing hydrogen
US3516263 *Mar 25, 1969Jun 23, 1970Atomic Energy CommissionMethod of storing hydrogen
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4079523 *Nov 8, 1976Mar 21, 1978The International Nickel Company, Inc.Air melting an iron charge
US4111689 *Feb 9, 1976Sep 5, 1978Franklin BaumgartnerTitanium-vanadium-iron and/or manganese alloy
US4133426 *Feb 24, 1978Jan 9, 1979The International Nickel Company, Inc.Hydride container
US4134490 *Feb 24, 1978Jan 16, 1979The International Nickel Company, Inc.Gas storage containment
US4134491 *Feb 24, 1978Jan 16, 1979The International Nickel Company, Inc.Means for storage of hydrogen gas
US4135621 *Feb 24, 1978Jan 23, 1979The International Nickel Company, Inc.Storage as metallic hydride
US4153484 *Jan 18, 1977May 8, 1979Matsushita Electric Industrial Co., Ltd.Alloys of titanium, zirconium, manganese
US4154364 *Dec 23, 1976May 15, 1979Shin-Etsu Chemical Co., Ltd.Thermally insulating containers for liquefied gases
US4160014 *May 10, 1978Jul 3, 1979Matsushita Electric Industrial Co., Ltd.Hydrogen storage material
US4163666 *Jan 31, 1978Aug 7, 1979Dan DavidovHydrogen charged alloys of Zr(A1-x Bx)2 and method of hydrogen storage
US4178987 *Jul 12, 1978Dec 18, 1979Standard Oil Company, A Corporation Of IndianaMoving bed hydride/dehydride systems
US4183369 *Nov 4, 1977Jan 15, 1980Thomas Robert EMethod of transmitting hydrogen
US4195989 *Oct 25, 1978Apr 1, 1980Matsushita Electric Industrial Co., Ltd.Titanium-manganese-metal alloy, crystal structure, hydriding
US4196525 *Aug 1, 1977Apr 8, 1980Johnson, Matthey & Co., LimitedFiber encapsulated intermettallic compound for absorption of hydrogen
US4200623 *Oct 25, 1978Apr 29, 1980Compagnie Francaise De RaffinageProcess for the preparation of a hydrogen reserve
US4200624 *Oct 25, 1978Apr 29, 1980Compagnie Francaise De RaffinageCombined hydrogen storage and production process
US4214699 *Apr 10, 1978Jul 29, 1980Daimler-Benz AktiengesellschaftParking heater and method using hydrides in motor vehicles powered by hydrogen
US4215008 *Jun 27, 1978Jul 29, 1980Shin-Etsu Chemical Co. Ltd.Adsorption
US4262739 *Jan 3, 1979Apr 21, 1981The United States Of America As Represented By The Department Of EnergySystem for thermal energy storage, space heating and cooling and power conversion
US4278466 *Nov 9, 1979Jul 14, 1981Battelle Memorial InstituteTitanium alloy composition and method for the storage of hydrogen
US4283226 *Nov 8, 1976Aug 11, 1981U.S. Philips CorporationActivation of alloy with hydrogen
US4305725 *Oct 20, 1980Dec 15, 1981Rca CorporationMethod of and apparatus for outgassing raw material used to grow crystals
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US4350673 *Feb 2, 1979Sep 21, 1982Matsushita Electric Industrial Company, LimitedMethod of storing hydrogen
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US4360445 *Jun 16, 1981Nov 23, 1982The United States Of America As Represented By The United States Department Of EnergyOxygen stabilized zirconium-vanadium-iron alloy
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Classifications
U.S. Classification34/416, 62/46.2, 148/DIG.153, 502/324, 423/644, 420/900, 423/248, 376/151, 420/581, 95/116
International ClassificationC22C14/00, F17C11/00, C01B3/00, H01M4/38
Cooperative ClassificationY02E60/327, Y10S420/90, Y10S148/153, H01M4/383, C22C14/00, Y02E60/321, F17C11/005, Y02E60/12, C01B3/0031
European ClassificationH01M4/38B, F17C11/00D, C22C14/00, C01B3/00D2F