Mg-Ni hydrogen storage composite having high storage capacity and excellent room temperature kinetics

Abstract

A hydrogen storage alloy having an atomically engineered microstructure that both physically and chemically absorbs hydrogen. The atomically engineered microstructure has a predominant volume of a first microstructure which provides for chemically absorbed hydrogen and a volume of a second microstructure which provides for physically absorbed hydrogen. The volume of the second microstructure may be at least 5 volume % of atomically engineered microstructure. The atomically engineered microstructure may include porous micro-tubes in which the porosity of the micro-tubes physically absorbs hydrogen. The micro-tubes may be at least 5 volume % of the atomically engineered microstructure. The micro-tubes may provide proton conduction channels within the bulk of the hydrogen storage alloy and the proton conduction channels may be at least 5 volume % of the atomically engineered microstructure.

Description

FILED OF THE INVENTION [0001] The instant invention relates generally to hydrogen storage materials and more specifically to a new composite hydrogen storage material having heretofore unheard of properties. Specifically the instant hydrogen storage material provides for a storage capacity of up to 4.86 weight percent hydrogen with a high adsorption rate at temperatures as low as 30° C. and an absorption pressure of less than about 150 PSI. The composite materials are light weight and absorb at least 3 weight percent in less than two minutes at 30° C. More remarkably, the composite materials also have the ability to fully desorb the stored hydrogen at temperatures as low as 250° C., an ability not heretofore seen in materials with such a high total storage capacity. Even more amazingly the same material can desorb 2.51 weight percent of the stored hydrogen at 90° C. and 1.2 weight percent at 30° C. In addition these material are relatively inexpensive and easy to produce. BACKGROUND...

AI Technical Summary

Benefits of technology

"The present invention is a new type of material that can store and release hydrogen, a process that occurs at low temperatures and pressure. The material is made up of a magnesium-nickel alloy with a coating of a catalytically active metal, such as iron or palladium, on its surface. The coating is very thin and the material has a high capacity for storing hydrogen. It can also desorb the stored hydrogen at low temperatures. The material is easy and inexpensive to produce. The alloy has a unique structure and contains various elements like magnesium, nickel, manganese, cobalt, and others. The material can absorb at least 3 weight percent of hydrogen at low pressure and has a high adsorption rate."

Problems solved by technology

One of the problems posed by the use of hydrogen is its storage and transportation.

Hydrogen may be stored under high pressure in steel cylinders, but this approach has the drawback of requiring hazardous and heavy containers which are difficult to handle (in addition to having a low storage capacity of about 1% by weight).

Hydrogen may also be stored in cryogenic containers, but this entails the disadvantages associated with the use of cryogenic liquids; such as, for example, the high cost of the containers, which also require careful handling.

Although this property and the relatively low price of magnesium make the MgH2—Mg seem the optimum hydrogen storage system for transportation, for hydrogen-powered vehicles that is, its unsatisfactory kinetics have prevented it from being used up to the present time.

It is known for instance that pure magnesium can be hydrided only under drastic conditions, and then only very slowly and incompletely.

Moreover, the hydrogen storage capacity of a magnesium reserve diminishes during the charging / discharging cycles.

The high temperature level and the high energy requirement for expelling the hydrogen have the effect that, for example, a motor vehicle with an internal combustion engine, cannot exclusively be operated from these alloys.

For example, this alloy can be titanium / iron hydride (a typical low-temperature hydride store) which can be operated at temperatures down to below 0° C. These low-temperature hydride alloys have the disadvantage of having a low hydrogen storage capacity.

In addition to this relatively low storage capacity, these alloys also have the disadvantage that the price of the alloy is very high when metallic vanadium is used.

Although alloys of this type have a greater storage capacity for hydrogen than the alloy according to U.S. Pat. No. 4,160,014, hereby incorporated by reference, they have the disadvantage that temperatures of at least 250° C. are necessary in order to completely expel the hydrogen.

However, a high discharge capacity, particularly at low temperatures, is frequently necessary in industry because the heat required for liberating the hydrogen from the hydride stores is often available only at a low temperature level.

Although these attempts did improve the kinetics somewhat, certain essential disadvantages have not yet been eliminated from the resulting systems.

Furthermore, the storage capacity of such systems are generally far below what would theoretically be expected for MgH2.

However, there were encountered problems during the adhesion and the distribution of the nickel over the magnesium surface.

The storage capacity per volume of material which is achieved through this magnesium-containing granulate does not, however, meet any high demands because of the quantity of magnesium copper which is required for the eutectic mixture.

A high desorption temperature (above, for example, 150° C.) severely limits the uses to which the system may be put.

The use by Matsumato et al of amorphous structure materials to achieve better desorption kinetics due to the non-flat hysteresis curve is an inadequate and partial solution.

The other problems found in crystalline hydrogen storage materials, particularly low useful hydrogen storage capacity at moderate temperature, remain.

This is in contrast to multi-component single phase host crystalline materials which generally have a very limited range of stoichiometry available.

A continuous range of control of chemical and structural modification of the thermodynamics and kinetics of such crystalline materials therefore is not possible.

One drawback to these disordered materials is that, in the past, some of the Mg based alloys have been difficult to produce.

Also, the most promising materials (i.e. magnesium based materials) were extremely difficult to make in bulk form.

That is, while thin-film sputtering techniques could make small quantities of these disordered alloys, there was no bulk preparation technique.

Conventional techniques like induction melting have been found to be inadequate for such purposes.

. . Indeed, when crystalline symmetry is destroyed, it becomes impossible to retain the same short-range order.

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