# Patent

## Title
Metal hydride fuel storage and method thereof

## Abstract

An apparatus having a first substrate having (1) a cavity, (2) one or more resistive heaters, and (3) one or more coatings forming a diffusion barrier to hydrogen; a second substrate having (1) an outlet valve comprising a pressure relief structure and (2) one or more coatings forming a diffusion barrier to hydrogen, wherein said second substrate is coupled to said first substrate forming a sealed volume in said cavity; a metal hydride material contained within said cavity; and a gas distribution system formed by coupling a microfluidic interconnect to said pressure relief structure. Additional apparatuses and methods are also disclosed.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. patent application Ser. No. 11/546,113 filed Oct. 10, 2006 and now issued as U.S. Pat. No. 7,527,659, which is a divisional of U.S. patent application Ser. No. 10/371,876 filed Feb. 21, 2003 now issued as U.S. Pat. No. 7,122,261, which are all incorporated herein by reference.


The United States Government has rights in this invention pursuant to Contract No. DE-AC52-07NA27344 between the United States Department of Energy and the Lawrence Livermore National Security, LLC for the operation of Lawrence Livermore National Laboratory.


BACKGROUND OF THE INVENTION
This invention relates to fuel cells. Work is commonly derived from fuel by a combustion process which uses the pressure of expanding gases to turn a turbine or move a reciprocating piston and, ultimately, to provide torque to a driveshaft. This torque is then usually used for propulsion or to generate electrical power. In the latter case, the electrical power is often reconverted into mechanical work.
SUMMARY OF THE INVENTION
An aspect of the invention includes: an apparatus comprising a first substrate having (1) a cavity, (2) one or more resistive heaters, and (3) one or more electrically isolating, heat conducting coatings; a second substrate having (1) an outlet comprising (a) a hydrogen permaselective membrane and (b) a thick film porous material that forms a pressure relief structure and (2) one or more electrically isolating, heat conducting coatings, wherein the second substrate is bonded to the first substrate forming a sealed volume within the cavity; and a metal hydride material contained within the cavity.
A further aspect of the invention includes a method comprising forming a first substrate having a cavity; positioning one or more resistive heaters in the cavity; coating the cavity and the resistive heaters with one or more materials that are capable of (1) electrically isolating the resistive heaters and (2) conducting heat; filling the cavity with a metal hydride material; forming a second substrate having (1) an outlet comprising (a) a hydrogen permaselective membrane and (b) a thick film porous material that forms a pressure relief structure and (2) one or more electrically isolating, heat conducting coatings; and sealing the cavity by bonding the second substrate to the first substrate.
Another aspect of the invention includes an apparatus comprising a first substrate having an array of cavities containing (1) one or more resistive heaters, and (2) one or more electrically isolating, heat conducting coatings; a second substrate having (1) an array of outlets each comprising (a) a hydrogen permaselective membrane and (b) a thick film porous material that forms a pressure relief structure and (2) one or more electrically isolating, heat conducting coatings, wherein the second substrate is bonded to the first substrate forming a sealed volume within the array of cavities; and a metal hydride material contained within the array of cavities.
Another aspect of the invention includes an apparatus comprising a first substrate having (1) a cavity, (2) one or more resistive heaters, and (3) one or more coatings forming a diffusion barrier to hydrogen; a second substrate having (1) an outlet valve comprising a pressure relief structure and (2) one or more coatings forming a diffusion barrier to hydrogen, wherein said second substrate is coupled to said first substrate forming a sealed volume in said cavity; a metal hydride material contained within said cavity; and a gas distribution system formed by coupling a microfluidic interconnect to said pressure relief structure.
Another aspect of the invention includes an apparatus comprising: a first substrate having an array of cavities containing (1) one or more resistive heaters, and (2) one or more electrically isolating, heat conducting coatings; a second substrate having (1) an array of outlets each comprising a pressure relief structure and (2) one or more electrically isolating, heat conducting coatings, wherein said second substrate is coupled to said first substrate forming a sealed volume in said array of cavities; and a metal hydride material contained in said array of cavities; and a gas distribution system formed by coupling a microfluidic interconnect to said pressure relief structure.
Another aspect of the invention includes an apparatus comprising: a first substrate having an array of cavities containing (1) one or more resistive heaters, and (2) one or more coatings forming a diffusion barrier to hydrogen; a second substrate having (1) an array of outlets each comprising a pressure relief structure and (2) one or more coatings forming a diffusion barrier to hydrogen, wherein said second substrate is coupled to said first substrate forming a sealed volume in said array of cavities; and a metal hydride material contained in said array of cavities; and a gas distribution system formed by coupling a microfluidic interconnect to said pressure relief structure.
Another aspect of the invention includes a method comprising: forming a first substrate having a cavity; positioning one or more resistive heaters in said cavity; coating said cavity and said resistive heaters with one or more materials that are capable of (1) electrically isolating said one or more resistive heaters and (2) conducting heat; and adding a metal hydride material to said cavity.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of a metal hydride fuel storage apparatus.



DETAILED DESCRIPTION
While metal hydride materials have demonstrated the ability to store hydrogen in percentages by weight ranging from 1-10%, the use of this material as a means to store hydrogen fuel for fuel cells and other power generating techniques has been limited, particularly for portable power applications. Typically, the metal hydride is processed as a pressed powder to retain the required porosity, and placed in a vessel made of stainless steel or other high strength material. The vessel has a center flow channel to which the hydrogen outgases and is delivered to the exterior of the container. The limitation to deployment of such storage containers for portable power applications is the power requirements of heating the mass of the containment vessel. The power requirements are not efficient compared to the energy stored as fuel.
Fuel cells disclosed in U.S. patent application Ser. Nos. 09/967,145, 10/261,353, 10/131,846, 10/261,353 assigned to the same assignee can be used in conjunction with the present invention and are all hereby incorporated by reference in their entirety.
Disclosed herein is a metal hydride fuel storage cartridge with integrated heaters. FIG. 1 shows one embodiment of the invention. Referring to FIG. 1, a metal hydride fuel storage cartridge 2 comprises: a cavity 4 in a substrate 6, one or more resistive heaters 8 in said cavity, a cavity coating 10 along said cavity of one or more materials which electrically isolate the resistor and the metal hydride volume (the interior of the cavity), readily conduct heat to uniformly heat the cavity, and provide a diffusion barrier to hydrogen over the temperature range required to outgas the hydrogen from the metal hydride material, a metal hydride material (e.g., Ni, Al, Pd, Ti, or other alloys thereof) 12, a cap 14 comprising a cap coating 10 of one or more materials which electrically isolate the resistor and the metal hydride volume (the interior of the cavity), readily conduct heat to uniformly heat the cavity, and provide a diffusion barrier to hydrogen over the temperature range required to outgas the hydrogen from the metal hydride material, an outlet 16 and an outlet valve 18 comprising a hydrogen permaselective membrane window 20 with a resistive heater (not shown) and a porous membrane pressure relief structure 22. The outlet valve is coupled directly to a microfluidic interconnect or other gas distribution system (not shown). An O-ring 24 made of a dense ceramic material can be used to seal the coupling. The substrates can comprise silicon, glass, plastic or ceramic. Coating 10 may comprise silicon dioxide, polymers (e.g., polyimide, poly methylmethacralate (PMMA)) and metals (e.g., copper or cobalt). The hydrogen permaselective membrane material comprises a high strength polymer (e.g., PMMA, Polyimide) and/or metal alloy (e.g., Pd, Ti) which enables selective gas permeation through the membrane as a function of temperature. The thickness and porosity of the thick film porous material that is formed over the membrane can be tailored to provide a pressure gradient such that the hydrogen flow at the exterior of the valve is at ambient pressure, thereby forming the porous membrane pressure relief structure.
Referring to FIG. 1, cavity 10 is formed using micromachining methods, for example, etching, molding or hot embossing. The cavity is coated and the coated cavity is then filled with a metal hydride material (e.g., Ni, Al, Pd, Ti, hydrides or hydrides of similar alloys) using thin/thick film materials synthesis techniques, for example, sol gel spin casting, dip coating, spray deposition or sputter deposition. Shadow masking or other patterning methods are used to selectively deposit the metal hydride in the cavity, completely filling the cavity volume. The cavity is sealed after filling by bonding (shown by arrows 26) cap 14 to substrate 6. The final volume of the sealed cavity is determined by the power requirement to heat the metal hydride with the integrated resistive heaters and outgas the hydrogen through the outlet valve. The cavity has enough strength to withstand 20-50 psi pressure as the hydride is heated. The outlet may be constructed on the cap as a microflow channel which can be formed through the cap using micromachining techniques. The valve is formed by positioning a hydrogen permaselective membrane window structure over the microflow channel outlet. The membrane is formed by bonding the appropriate layer over the window. Additionally, the porous membrane pressure relief structure is formed over the membrane window by or coating the layers first, then etching the window from the backside selectively. The thickness and porosity of the porous membrane pressure relief structure can be tailored by control of the baking temperature and coating speed for solgel deposited processes, or the temperature and pressure of deposition for vacuum processes. The O-ring can be aligned to a pre-positioned cavity in a gas manifold system, wherein the alignment can be achieved through a package design in order to provide a modular and replaceable cartridge.
Additionally, the hydride storage cavities can be fabricated in arrays to provide more fuel storage capacity while optimizing the power needed to extract the hydrogen fuel from the cartridge. For applications to miniature fuel cells, effective heat transfer from the fuel cell heat source can also be used as a means to sustain the heat required to remove the hydrogen fuel from the cartridge.
All numbers expressing quantities of ingredients, constituents, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about”. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the subject matter presented herein are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
While particular operational sequences, materials, temperatures, parameters, and particular embodiments have been described and or illustrated, such are not intended to be limiting. Modifications and changes may become apparent to those skilled in the art, and it is intended that the invention be limited only by the scope of the appended claims.

## Claims

1. An apparatus comprising: a first substrate having (1) a cavity, (2) one or more resistive heaters, and (3) one or more coatings forming a diffusion barrier to hydrogen; a second substrate having (1) an outlet valve comprising a pressure relief structure and (2) one or more coatings forming a diffusion barrier to hydrogen, wherein said second substrate is coupled to said first substrate forming a sealed volume in said cavity; a metal hydride material contained within said cavity; and a gas distribution system formed by coupling a microfluidic interconnect to said pressure relief structure.

2. The apparatus recited in claim 1, wherein said first substrate comprises at least one of silicon, glass, plastic and ceramic.

3. The apparatus recited in claim 1, wherein said second substrate comprises at least one of silicon, glass, plastic and ceramic.

4. The apparatus recited in claim 1, wherein said cavity has enough strength to withstand 20-50 psi pressure as the hydride is heated.

5. The apparatus recited in claim 1, wherein the volume of said cavity is predetermined based on the power requirement to heat the metal hydride with said resistive heaters and outgas the hydrogen through said outlet valve.

6. The apparatus recited in claim 1, wherein said coatings comprises silicon dioxide, polymers, metals, or mixtures thereof.

7. The apparatus recited in claim 1, wherein the pressure relief structure comprises a hydrogen permaselective membrane, wherein said hydrogen permaselective membrane comprises a polymer and/or metal alloy material that enables selective gas permeation through the membrane as a function of temperature.

8. The apparatus recited in claim 1, wherein the pressure relief structure comprises a porous material, wherein said porous material is selected from a group consisting of nickel, silicon, silicon dioxide, silicon nitride, aluminum, alumina, polyimide, palladium, titanium, or alloys thereof.

9. The apparatus recited in claim 1, wherein the pressure relief structure comprises a porous material, wherein a thickness and porosity of said porous material is tailored to provide a pressure gradient such that a hydrogen flow at the outlet valve is at ambient pressure.

10. The apparatus recited in claim 1, wherein the pressure relief structure comprises a porous material, wherein said coupling is accomplished by placing an O-ring around said porous material.

11. The apparatus recited in claim 10, wherein said O-ring is a ceramic material.

12. The apparatus recited in claim 1, wherein said coupling comprises a seal.

13. An apparatus comprising: a first substrate having an array of cavities containing (1) one or more resistive heaters, and (2) one or more electrically isolating, heat conducting coatings; a second substrate having (1) an array of outlets each comprising a pressure relief structure and (2) one or more electrically isolating, heat conducting coatings, wherein said second substrate is coupled to said first substrate forming a sealed volume in said array of cavities; and a metal hydride material contained in said array of cavities; and a gas distribution system formed by coupling a microfluidic interconnect to said pressure relief structure.

14. The apparatus recited in claim 13, wherein each pressure relief structure comprises a porous material and a hydrogen permaselective membrane.

15. The apparatus recited in claim 13, wherein at least one of the substrates comprises at least one of silicon, glass, plastic and ceramic.

16. The apparatus recited in claim 13, wherein said cavity has enough strength to withstand 20-50 psi pressure as the hydride is heated.

17. The apparatus recited in claim 13, wherein said coatings comprise silicon dioxide, polymers, metals, or mixtures thereof.

18. The apparatus recited in claim 13, wherein the pressure relief structure comprises a hydrogen permaselective membrane, wherein said hydrogen permaselective membrane comprises a polymer and/or metal alloy material that enables selective gas permeation through the membrane as a function of temperature.

19. The apparatus recited in claim 13, wherein the pressure relief structure comprises a porous material, wherein said porous material is selected from a group consisting of nickel, silicon, silicon dioxide, silicon nitride, aluminum, alumina, polyimide, palladium, titanium, or alloys thereof.

20. The apparatus recited in claim 13, wherein the pressure relief structure comprises a porous material, wherein a thickness and porosity of said porous material is tailored to provide a pressure gradient such that a hydrogen flow at the outlet valve is at ambient pressure.

21. The apparatus recited in claim 13, wherein the pressure relief structure comprises a porous material, wherein said coupling is accomplished by placing an O-ring around said porous material.

22. An apparatus comprising: a first substrate having an array of cavities containing (1) one or more resistive heaters, and (2) one or more coatings forming a diffusion barrier to hydrogen; a second substrate having (1) an array of outlets each comprising a pressure relief structure and (2) one or more coatings forming a diffusion barrier to hydrogen, wherein said second substrate is coupled to said first substrate forming a sealed volume in said array of cavities; and a metal hydride material contained in said array of cavities; and a gas distribution system formed by coupling a microfluidic interconnect to said pressure relief structure.

23. A method comprising:
forming a first substrate having a cavity;
positioning one or more resistive heaters in said cavity;
coating said cavity and said resistive heaters with one or more materials that are capable of (1) electrically isolating said one or more resistive heaters and (2) conducting heat; and
adding a metal hydride material to said cavity.

24. The method recited in claim 23, further comprising bonding a cap to the first substrate for sealing said cavity.