US20060188762A1 - Thermally efficient hydrogen storage system - Google Patents
Thermally efficient hydrogen storage system Download PDFInfo
- Publication number
- US20060188762A1 US20060188762A1 US11/399,920 US39992006A US2006188762A1 US 20060188762 A1 US20060188762 A1 US 20060188762A1 US 39992006 A US39992006 A US 39992006A US 2006188762 A1 US2006188762 A1 US 2006188762A1
- Authority
- US
- United States
- Prior art keywords
- hydrogen
- container
- hydrogen generator
- endothermic
- exothermic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 182
- 239000001257 hydrogen Substances 0.000 title claims abstract description 181
- 229910052987 metal hydride Inorganic materials 0.000 claims abstract description 15
- 150000004681 metal hydrides Chemical class 0.000 claims abstract description 15
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000012546 transfer Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 150000004678 hydrides Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- -1 lithium aluminum tetrahydride Chemical compound 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 55
- 238000000034 method Methods 0.000 abstract description 37
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 239000002918 waste heat Substances 0.000 abstract description 7
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000007246 mechanism Effects 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 230000001105 regulatory effect Effects 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000012448 Lithium borohydride Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- KJLLKLRVCJAFRY-UHFFFAOYSA-N mebutizide Chemical compound ClC1=C(S(N)(=O)=O)C=C2S(=O)(=O)NC(C(C)C(C)CC)NC2=C1 KJLLKLRVCJAFRY-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
-
- 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with 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
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Definitions
- the disclosed methods and apparatus relate to the field of hydrogen storage systems.
- the methods and apparatus relate to hydrogen storage using both endothermic and exothermic hydrogen generators.
- Fuel cells that generate electrical power using reactions between hydrogen and an oxidizing gas such as oxygen or air are well known in the art.
- Such fuel cells require a source of hydrogen, such as a compressed hydrogen gas cylinder, a liquefied hydrogen tank, a hydrogen storage powder, a hydrogen storage alloy, a hydride such as lithium or sodium borohydride, a metal hydride or a reformed hydrocarbon such as natural gas or methane.
- the typical fuel cell has a single source of hydrogen, which may be produced by either exothermic or endothermic processes.
- present fuel cells may generate more waste heat than usable electrical energy.
- fuel cells are used to power small, portable electronic devices such as cell phones, laptop computers, video cameras, flashlights, portable electrical tools, personal digital assistants, etc.
- the production of large amounts of waste heat can create problems with overheating of the electronic device or with excessively hot hand-held devices.
- the incorporation of a hydrogen fuel cell that produces additional waste heat creates serious problems with thermal control.
- FIG. 1 illustrates an exemplary apparatus (not to scale) comprising exothermic and endothermic hydrogen generators.
- FIG. 2 illustrates another exemplary apparatus (not to scale) comprising exothermic and endothermic hydrogen generators, a fuel cell and a portable electronic device.
- exothermic and endothermic are used according to their plain and ordinary meanings. Generally, an “exothermic” process or reaction is one that releases heat to its environment, while an “endothermic” process or reaction is one that absorbs heat from its environment.
- an exothermic hydrogen generator will transfer heat to an endothermic hydrogen generator, while an endothermic hydrogen generator will absorb heat from an exothermic hydrogen generator during hydrogen generation.
- an endothermic hydrogen generator may also absorb heat from other sources, such as a fuel cell.
- the term “about” when applied to a number means within plus or minus five percent of that number. For example, “about 100” means any number between 95 and 105.
- the term “approximately” means within ten percent of a value. For example, “approximately equal” would mean that a first value is within plus or minus ten percent of a second value.
- an “electronic device” comprises any device and/or apparatus that may derive part or all of its power supply from a hydrogen based fuel cell.
- a “portable electronic device” is one that may be moved from one location to another by a person. In some embodiments of the invention, a “portable electronic device” may be carried by a person. In certain embodiments of the invention, a “portable electronic device” may be a hand-held device.
- “Portable electronic devices” include, but are not limited to, cell phones, laptop computers, video cameras, flashlights, portable electrical tools and personal digital assistants.
- two or more components are “operably coupled” when there are one or more connections between the components that allow or facilitate their functional interaction.
- a hydrogen generator would be “operably coupled” to a fuel cell when there is a functional attachment that allows hydrogen from the hydrogen generator to be used by the fuel cell to generate electrical power.
- a fuel cell would be “operably coupled” to an electronic device when there is a functional attachment that allows electrical power generated by the fuel cell to be used to power the electronic device.
- Certain embodiments of the invention concern fuel cells comprising both endothermic and exothermic hydrogen generators.
- the principles underlying hydrogen based fuel cells have been known since the experiments of William Grove in 1839.
- a variety of hydrogen utilizing fuel cell designs are known in the art, including but not limited to the polymer electrolyte membrane (PEM) fuel cell, the phosphoric acid fuel cell, the molten carbonate fuel cell and the solid oxide fuel cell.
- PEM polymer electrolyte membrane
- the methods and apparatus disclosed herein are not limited as to the type of fuel cell, so long as the fuel cell utilizes hydrogen.
- Different fuel cells are designed to function at different operating temperatures.
- fuel cells designed to operate at near ambient temperatures such as PEM fuel cells, may be used in the disclosed methods and apparatus.
- the electrochemical reactions underlying hydrogen fuel cells are known. Once hydrogen is produced, it is provided to the anode side of the fuel cell, where it encounters a catalyst, such as platinum.
- the catalyst facilitates the removal of electrons from hydrogen, creating H + ions.
- the electrons travel through an external circuit to the cathode side of the fuel cell, providing electrical power.
- H + electrons and oxygen react to create water. Waste heat is also produced as a byproduct of the electrochemical processes.
- the charge carrier species in PEM fuel cells and phosphoric acid fuel cells is H + , which diffuses from the anode to the cathode through an electrolyte.
- Carbonate fuel cells involve an intermediary process, in which oxygen reacts with electrons and carbon dioxide at the cathode to produce CO 3 ⁇ 2 .
- the CO 3 ⁇ 2 passes through an electrolyte to the anode, where it reacts with hydrogen to form water and carbon dioxide, releasing two electrons.
- solid oxide fuel cells another intermediary process results in the cathodic formation of O ⁇ 2 , which reacts with hydrogen at the anode to form water and release electrons.
- the voltage difference generated by a single fuel cell is limited to about 1.2 volts per electrode pair (anode plus cathode). It is contemplated that the apparatus and methods disclosed herein may utilize single fuel cells or multiple fuel cells that are connected in series to provide any level of voltage required to operate an associated electronic device.
- Various embodiments of the invention comprise both exothermic and endothermic hydrogen generators.
- the claimed methods and apparatus are not limiting as to the particular exothermic or endothermic hydrogen generators used. Rather, it is contemplated that any exothermic hydrogen generator known in the art could be used with any known endothermic hydrogen generator.
- exothermic hydrogen generators include but are not limited to borohydride (e.g., sodium borohydride or lithium borohydride) solutions exposed to a catalyst such as platinum, solid hydrides exposed to water at elevated temperature, hydrogen generators that utilize partial oxidation (POX) reformation of natural gas, methane or other hydrocarbons, and other catalytic hydrogen generators.
- borohydride e.g., sodium borohydride or lithium borohydride
- PX partial oxidation
- Exothermic hydrogen generators comprising a borohydride, such as lithium or sodium borohydride, are known in the art (see, e.g., U.S. Pat. Nos. 4,000,003; 4,002,726; 4,628,010; 5,372,617).
- Borohydride based hydrogen generators may be obtained from commercial sources, such as Millenium Cell, Inc. (Eatontown, N.J.).
- an appropriate catalyst such as platinum
- aqueous borohydride solutions react with water to generate hydrogen and borate.
- the borate can be recycled to regenerate borohydride (U.S. Pat. No. 4,002,726).
- the catalyst may be in the form of a solid metal object, a perforated metal object, a metal coated object, a metal mesh, a metal sponge, metal wires or metal coated wires, an aggregate of metal particles or metal coated particles, or any other form known in the art.
- production of hydrogen through exothermic reaction of borohydrides may be controlled by regulating exposure of the catalyst to the borohydride solution.
- a bimetallic, temperature-sensitive control mechanism could reversibly place a non-catalytic metal (or non-metal) sheath between the platinum and the borohydride solution to regulate the generation of heat by the exothermic process.
- the control mechanism could be regulated to limit the rate of exothermic hydrogen production to the fuel cell by the demand for electrical power of an attached electronic device.
- Such control mechanisms and other features of borohydride based hydrogen generators are known in the art. It is contemplated that any such known apparatus and methods may be used in the practice of the claimed subject matter.
- Hydrogen generators based on reformation of hydrocarbons are well known (e.g., U.S. Pat. Nos. 5,601,937; 5,928,805; 6,267,792; 6,318,306). Hydrogen generation by reformation of hydrocarbons, such as natural gas, can be either exothermic or endothermic, depending on the process used. Steam reformation of hydrocarbons with water vapor results in endothermic hydrogen generation, while partial oxidation (POX) reformation with a burner or catalyst results in exothermic hydrogen generation.
- An exemplary exothermic hydrogen generator would comprise POX reformation of hydrocarbons.
- Certain hydrogen generators based on hydrocarbon reformation are designed to operate at very high temperatures.
- the endothermic hydrogen generator disclosed in U.S. Pat. No. 5,601,937 operates at a temperature of between 600 and 800° C.
- the skilled artisan will realize that such high temperature hydrogen generators are generally not suitable for use with portable electronic devices.
- endothermic hydrogen generators utilize metal hydrides that can reversibly adsorb or release hydrogen gas. Hydrogen uptake by such metal hydrides is an exothermic process. Hydrogen release is endothermic and can be activated by heating the metal hydride, decreasing the external pressure or irradiating the metal hydride with a laser.
- Metal hydride based hydrogen generators are one of the most commonly used hydrogen generation systems (e.g., U.S. Pat. Nos. 4,211,537; 4,728,580; 4,667,185; 6,165,643). Endothermic hydrogen generation using metal hydride or metal alloy hydrides is well known (U.S. Pat. Nos. 4,302,217; 4,537,761; 4,570,446; 4,599,867; 5,360,461; 5,797,269; 5,962,155; 5,987,895; 6,143,052; 6,194,092; 6,267,229). Any such hydride based endothermic hydrogen generator may be used in the methods and apparatus disclosed herein.
- an endothermic hydrogen generator comprises carbon nanotube hydrogen storage systems (e.g., Dillon et al., “Carbon Nanotube Materials for Hydrogen Storage,” Proceedings of the 2001 DOE Hydrogen Program Review, http://www.eren.doe.gov/hydrogen/pdfs/30535am.pdf).
- carbon nanotube hydrogen storage systems e.g., Dillon et al., “Carbon Nanotube Materials for Hydrogen Storage,” Proceedings of the 2001 DOE Hydrogen Program Review, http://www.eren.doe.gov/hydrogen/pdfs/30535am.pdf.
- single-walled carbon nanotubes can reportedly store up to 7 weight percent of hydrogen gas. It is suggested that semi-conducting carbon nanotubes are capable of storing more hydrogen than metallic nanotubes. Methods for preparing carbon nanotubes are well known (e.g., U.S. Pat. Nos. 6,258,401; 6,283,812; 6,297,592).
- Carbon nanotubes may also be obtained from commercial sources, such as CarboLex (Lexington, Ky.), NanoLab (Watertown, Mass.), Materials and Electrochemical Research (Tucson, Ariz. or Carbon Nano Technologies Inc. (Houston, Tex.). Methods of adsorption and desorption of hydrogen from carbon nanotubes, suitable for use in the presently disclosed methods and apparatus, are disclosed in Dillon et al. (2001).
- endothermic hydrogen generators may comprise tanks containing compressed hydrogen gas or liquid hydrogen. Expansion of compressed gas or conversion of liquid hydrogen to gaseous hydrogen are endothermic processes that may be used in the disclosed methods and apparatus.
- an endothermic hydrogen generator is disclosed in U.S. Pat. No. 5,601,937, discussed above in connection with hydrocarbon reformation. Catalytic decomposition of methanol into hydrogen and carbon monoxide is also an endothermic process
- the rate of exothermic and/or endothermic hydrogen generation may be regulated by various control mechanisms.
- a variety of mechanisms for regulating hydrogen generators are known (e.g., U.S. Pat. Nos. 4,211,537; 4,302,217; 5,372,617; 5,702,491; 5,797,269; 5,987,895; 6,267,792). Any known control mechanism for regulating hydrogen generation may be used in the disclosed methods and apparatus.
- Such control mechanisms may be either active or passive in nature.
- a requirement for electrical power such as turning on an electrical device powered by a fuel cell, could serve as a signal to initiate exposure of a platinum catalyst to an aqueous borohydride solution, initiating exothermic hydrogen production.
- the amount of hydrogen and electrical power generated will be directly correclated to the surface area of the catalyst exposed to the borohydride solution.
- Heat released by the exothermic process could be passively transferred to an endothermic hydrogen generator, such as a metal hydride.
- heat transfer may be facilitated by incorporation of heat transfer mechanisms, such as radiative fins, liquid filled tubes or a heat conductive material such as aluminum or copper.
- Absorption of heat by a metal hydride would initiate endothermic hydrogen production.
- the rate of endothermic hydrogen production may be passively controlled by the rate of heat generation from exothermic hydrogen production.
- an external heat source such as a resistive electrical heater, may be used.
- waste heat generated by a fuel cell such as a PEM fuel cell, could be transferred to an endothermic hydrogen generator to provide an additional source of heat.
- the electrical power generated by a hydrogen fuel cell may be supplemented by an additional battery.
- This additional source of electrical power could be used, for example, to assist in the initiation of hydrogen production, such as by powering a heater to facilitate endothermic hydrogen production, by opening or closing valves or covers to regulate exposure of a borohydride solution to a catalyst or to regulate the amount of water or water vapor added to a chemical hydride.
- the control mechanism for regulating the amount of catalyst exposed to borohydride solution may receive input from one or more temperature sensors, such as a thermistor, that monitors the temperature of the exothermic hydrogen generator, the endothermic hydrogen generator or the fuel cell compartment.
- the control mechanism may incorporate a microprocessor, microcontroller or other control mechanism that prevents the temperature from exceeding predetermined limits.
- a more active mechanism of regulating hydrogen generation may be used.
- Such a mechanism could control the rates of both exothermic and endothermic hydrogen production to more precisely control the overall temperature of the hydrogen storage system, fuel cell or electronic device.
- the rates of endothermic and exothermic hydrogen generation may be balanced to provide an overall thermally neutral hydrogen generation, or even a net endothermic hydrogen generation.
- a microcontroller or other control mechanism could regulate the rates of endothermic and/or exothermic hydrogen generation to maintain a selected temperature of the hydrogen storage system, fuel cell and/or electronic device.
- the temperature of the hydrogen storage system could be controlled to correspond to the ambient temperature of the environment.
- any accessory mechanisms, devices or components appropriate for control of the hydrogen generators including without limitation valves, pumps, covers, relief valves, sensors, thermistors, microcontrollers, controllers, microprocessors, displays, readouts, manifolds, etc. may be used in the disclosed methods and apparatus.
- FIG. 1 discloses an exemplary embodiment of the invention comprising a thermally efficient hydrogen storage system 100 .
- the system 100 comprises a first compartment 110 containing a first hydrogen generator 120 . Inside the first compartment 110 is a second compartment 130 containing a second hydrogen generator 140 . Both the first and second compartments ( 110 , 130 ) are connected through ports ( 160 , 170 ) to an external device, such as a fuel cell. The ports ( 160 , 170 ) allow for the passage of hydrogen gas from the hydrogen generators ( 120 , 140 ) to the external device.
- the ports ( 160 , 170 ) may incorporate filters.
- filters In exemplary embodiments of the invention, porous metal filters or porous polytetrafluoroethylene films may be used. However, any filter that allows the free passage of hydrogen gas, while preventing movement of the components of the hydrogen generators ( 120 , 140 ), may be used.
- the movement of hydrogen may be regulated by various valves, pumps or other control mechanisms, as disclosed above.
- the rates of hydrogen generation by the first ( 120 ) and/or second ( 140 ) hydrogen generators may also be regulated by various control mechanisms, as disclosed above.
- the hydrogen generators ( 120 , 140 ) may be reversible. That is, depending on the hydrogen generators ( 120 , 140 ) used, it may be possible to recharge the hydrogen storage system 100 with hydrogen after the system 100 has been discharged.
- the ports ( 160 , 170 ) may serve as hydrogen recharge ports, allowing uptake of hydrogen into the first and second compartments ( 110 , 130 ).
- the first compartment 110 contains an endothermic hydrogen generator 120 , comprising a metal hydride that has been charged with hydrogen gas.
- the second compartment 130 contains an exothermic hydrogen generator 140 , comprising an aqueous solution of sodium borohydride and a catalyst, for example, platinum.
- an exothermic hydrogen generator 140 comprising an aqueous solution of sodium borohydride and a catalyst, for example, platinum.
- heat is produced and is transferred to the first compartment 110 .
- This transfer of heat 150 results in the release of hydrogen from the metal hydride 120 , which requires input of heat in order to produce hydrogen. Since the heat produced by the exothermic hydrogen generator 140 is largely absorbed by the operation of the endothermic hydrogen generator 120 , the net release of heat 180 by the hydrogen storage system 100 is low.
- the rates of exothermic and/or endothermic hydrogen production may be controlled so that the hydrogen storage system 100 is thermally neutral.
- heat released 150 by the exothermic hydrogen generator 140 is balanced by heat absorbed by the endothermic hydrogen generator 120 .
- the first compartment 110 may be enclosed by a container composed of materials of low thermal conductivity to increase the efficiency of heat absorption by the endothermic hydrogen generator 120 . Such materials are well known in the art.
- the efficiency of heat transfer between the first 110 and second 130 compartments may be increased by using any known method of heat transfer.
- the container enclosing the inner, second compartment 130 may be comprised in whole or in part of a substance with a relatively high heat conductance, such as copper or aluminum. Heat transfer may be increased by the addition of metal fins extending into the first 110 and/or second compartment 130 .
- tubes filled with a heat conducting liquid may extend through the first 110 and/or second compartment 130 .
- the tubes may or may not have fins or other projections attached to increase the efficiency of heat transfer.
- Various methods and designs to increase heat transfer in hydrogen generators are known (see, e.g., U.S. Pat. Nos. 4,211,537; 4,302,217; 4,570,446; 4,599,867; 5,962,155; 6,194,092; 6,267,229), any of which may be used in the methods and apparatus disclosed herein.
- FIG. 2 illustrates another exemplary embodiment of the invention.
- a portable electronic device 260 comprises at least one exothermic hydrogen generator 210 and at least one endothermic hydrogen generator 220 .
- the exothermic 210 and endothermic 220 hydrogen generators are operably coupled to a fuel cell 230 , to provide hydrogen to the fuel cell 230 .
- the fuel cell 230 may be any fuel cell 230 known in the art that utilizes hydrogen to produce electrical power.
- Certain embodiments of the invention comprise a fuel cell 230 designed to operate at near ambient temperature.
- the fuel cell 230 comprises positive 240 and negative 250 terminals.
- the fuel cell 230 is operably coupled to the portable electronic device 260 to provide electrical power to the portable electronic device 260 .
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The present disclosure concerns methods and apparatus comprising both exothermic and endothermic hydrogen generators. In certain embodiments of the invention, such hydrogen generators may be used to provide hydrogen fuel to a fuel cell. The use of both exothermic and endothermic hydrogen generators is advantageous for providing thermally efficient hydrogen storage systems that reduce or eliminate the formation of waste heat resulting from hydrogen generation. In some embodiments of the invention, the exothermic hydrogen generator comprises a sodium borohydride hydrogen generator and the endothermic hydrogen generator comprises a metal hydride storage system. In various embodiments of the invention, the rates of exothermic and/or endothermic hydrogen generation may be controlled. Control of exothermic and/or endothermic hydrogen generation may provide endothermic or thermally neutral hydrogen production. In certain embodiments of the invention, the thermally efficient hydrogen storage system may be used to provide electrical power to a portable electronic device.
Description
- The disclosed methods and apparatus relate to the field of hydrogen storage systems. In particular, the methods and apparatus relate to hydrogen storage using both endothermic and exothermic hydrogen generators.
- Fuel cells that generate electrical power using reactions between hydrogen and an oxidizing gas such as oxygen or air are well known in the art. Such fuel cells require a source of hydrogen, such as a compressed hydrogen gas cylinder, a liquefied hydrogen tank, a hydrogen storage powder, a hydrogen storage alloy, a hydride such as lithium or sodium borohydride, a metal hydride or a reformed hydrocarbon such as natural gas or methane. The typical fuel cell has a single source of hydrogen, which may be produced by either exothermic or endothermic processes.
- Depending on their efficiency, present fuel cells may generate more waste heat than usable electrical energy. For applications where fuel cells are used to power small, portable electronic devices such as cell phones, laptop computers, video cameras, flashlights, portable electrical tools, personal digital assistants, etc. the production of large amounts of waste heat can create problems with overheating of the electronic device or with excessively hot hand-held devices. As many electronic devices generate waste heat by their operation, the incorporation of a hydrogen fuel cell that produces additional waste heat creates serious problems with thermal control.
- The following drawings form part of the present specification and are included to further demonstrate certain embodiments of the invention. The embodiments may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments of the invention presented herein.
-
FIG. 1 illustrates an exemplary apparatus (not to scale) comprising exothermic and endothermic hydrogen generators. -
FIG. 2 illustrates another exemplary apparatus (not to scale) comprising exothermic and endothermic hydrogen generators, a fuel cell and a portable electronic device. - As used herein, “a” or “an” may mean one or more than one of an item.
- The terms “exothermic” and “endothermic” are used according to their plain and ordinary meanings. Generally, an “exothermic” process or reaction is one that releases heat to its environment, while an “endothermic” process or reaction is one that absorbs heat from its environment. Within the context of the present disclosure, an exothermic hydrogen generator will transfer heat to an endothermic hydrogen generator, while an endothermic hydrogen generator will absorb heat from an exothermic hydrogen generator during hydrogen generation. In certain embodiments of the invention, an endothermic hydrogen generator may also absorb heat from other sources, such as a fuel cell.
- As used herein, the term “about” when applied to a number means within plus or minus five percent of that number. For example, “about 100” means any number between 95 and 105.
- As used herein, the term “approximately” means within ten percent of a value. For example, “approximately equal” would mean that a first value is within plus or minus ten percent of a second value.
- As used herein, an “electronic device” comprises any device and/or apparatus that may derive part or all of its power supply from a hydrogen based fuel cell. A “portable electronic device” is one that may be moved from one location to another by a person. In some embodiments of the invention, a “portable electronic device” may be carried by a person. In certain embodiments of the invention, a “portable electronic device” may be a hand-held device. “Portable electronic devices” include, but are not limited to, cell phones, laptop computers, video cameras, flashlights, portable electrical tools and personal digital assistants.
- As used herein, two or more components are “operably coupled” when there are one or more connections between the components that allow or facilitate their functional interaction. For example, a hydrogen generator would be “operably coupled” to a fuel cell when there is a functional attachment that allows hydrogen from the hydrogen generator to be used by the fuel cell to generate electrical power. Similarly, a fuel cell would be “operably coupled” to an electronic device when there is a functional attachment that allows electrical power generated by the fuel cell to be used to power the electronic device.
- Fuel Cells
- Certain embodiments of the invention concern fuel cells comprising both endothermic and exothermic hydrogen generators. The principles underlying hydrogen based fuel cells have been known since the experiments of William Grove in 1839. A variety of hydrogen utilizing fuel cell designs are known in the art, including but not limited to the polymer electrolyte membrane (PEM) fuel cell, the phosphoric acid fuel cell, the molten carbonate fuel cell and the solid oxide fuel cell. The methods and apparatus disclosed herein are not limited as to the type of fuel cell, so long as the fuel cell utilizes hydrogen. Different fuel cells are designed to function at different operating temperatures. In some embodiments of the invention, fuel cells designed to operate at near ambient temperatures, such as PEM fuel cells, may be used in the disclosed methods and apparatus.
- The electrochemical reactions underlying hydrogen fuel cells are known. Once hydrogen is produced, it is provided to the anode side of the fuel cell, where it encounters a catalyst, such as platinum. The catalyst facilitates the removal of electrons from hydrogen, creating H+ ions. The electrons travel through an external circuit to the cathode side of the fuel cell, providing electrical power. At the cathode, H+, electrons and oxygen react to create water. Waste heat is also produced as a byproduct of the electrochemical processes.
- Variations on this basic scheme are well known. The charge carrier species in PEM fuel cells and phosphoric acid fuel cells is H+, which diffuses from the anode to the cathode through an electrolyte. Carbonate fuel cells involve an intermediary process, in which oxygen reacts with electrons and carbon dioxide at the cathode to produce CO3 −2. The CO3 −2 passes through an electrolyte to the anode, where it reacts with hydrogen to form water and carbon dioxide, releasing two electrons. In solid oxide fuel cells, another intermediary process results in the cathodic formation of O−2, which reacts with hydrogen at the anode to form water and release electrons. These and any other known type of hydrogen utilizing fuel cells are all contemplated for use in the methods and apparatus disclosed herein.
- The voltage difference generated by a single fuel cell is limited to about 1.2 volts per electrode pair (anode plus cathode). It is contemplated that the apparatus and methods disclosed herein may utilize single fuel cells or multiple fuel cells that are connected in series to provide any level of voltage required to operate an associated electronic device.
- Hydrogen Generators
- Various embodiments of the invention comprise both exothermic and endothermic hydrogen generators. The claimed methods and apparatus are not limiting as to the particular exothermic or endothermic hydrogen generators used. Rather, it is contemplated that any exothermic hydrogen generator known in the art could be used with any known endothermic hydrogen generator.
- Exothermic Hydrogen Generators
- A variety of exothermic hydrogen generators are known. These include but are not limited to borohydride (e.g., sodium borohydride or lithium borohydride) solutions exposed to a catalyst such as platinum, solid hydrides exposed to water at elevated temperature, hydrogen generators that utilize partial oxidation (POX) reformation of natural gas, methane or other hydrocarbons, and other catalytic hydrogen generators.
- Exothermic hydrogen generators comprising a borohydride, such as lithium or sodium borohydride, are known in the art (see, e.g., U.S. Pat. Nos. 4,000,003; 4,002,726; 4,628,010; 5,372,617). Borohydride based hydrogen generators may be obtained from commercial sources, such as Millenium Cell, Inc. (Eatontown, N.J.). In the presence of an appropriate catalyst, such as platinum, aqueous borohydride solutions react with water to generate hydrogen and borate. The borate can be recycled to regenerate borohydride (U.S. Pat. No. 4,002,726). In various embodiments of the invention, the catalyst may be in the form of a solid metal object, a perforated metal object, a metal coated object, a metal mesh, a metal sponge, metal wires or metal coated wires, an aggregate of metal particles or metal coated particles, or any other form known in the art.
- In certain embodiments of the invention, production of hydrogen through exothermic reaction of borohydrides may be controlled by regulating exposure of the catalyst to the borohydride solution. For example, a bimetallic, temperature-sensitive control mechanism could reversibly place a non-catalytic metal (or non-metal) sheath between the platinum and the borohydride solution to regulate the generation of heat by the exothermic process. In alternative embodiments of the invention, the control mechanism could be regulated to limit the rate of exothermic hydrogen production to the fuel cell by the demand for electrical power of an attached electronic device. Such control mechanisms and other features of borohydride based hydrogen generators are known in the art. It is contemplated that any such known apparatus and methods may be used in the practice of the claimed subject matter.
- An alternative embodiment of a borohydride based hydrogen generator is disclosed in U.S. Pat. No. 4,628,010, which shows hydrogen generation by reaction of lithium borohydride with iron oxide. In other alternative embodiments of the invention, solid chemical hydrides such as lithium borohydride, sodium borohydride, calcium hydride, lithium aluminum hydride or lithium hydride generate hydrogen upon exposure to water (U.S. Pat. Nos. 4,000,003; 5,372,617; 5,702,491). In certain embodiments of the invention, hydrogen generation proceeds more efficiently at elevated temperature (U.S. Pat. No. 5,372,617).
- Another exemplary exothermic hydrogen generator is disclosed in U.S. Pat. No. 6,274,093, comprising a compound such as ammonia that can react with a solid compound, such as lithium aluminum tetrahydride, to release hydrogen. The rate of the reaction (and the corresponding rate of hydrogen production) can be controlled by regulating the flow of ammonia to a reactor containing the tetrahydride.
- Hydrogen generators based on reformation of hydrocarbons are well known (e.g., U.S. Pat. Nos. 5,601,937; 5,928,805; 6,267,792; 6,318,306). Hydrogen generation by reformation of hydrocarbons, such as natural gas, can be either exothermic or endothermic, depending on the process used. Steam reformation of hydrocarbons with water vapor results in endothermic hydrogen generation, while partial oxidation (POX) reformation with a burner or catalyst results in exothermic hydrogen generation. An exemplary exothermic hydrogen generator would comprise POX reformation of hydrocarbons.
- Certain hydrogen generators based on hydrocarbon reformation are designed to operate at very high temperatures. For example, the endothermic hydrogen generator disclosed in U.S. Pat. No. 5,601,937 operates at a temperature of between 600 and 800° C. The skilled artisan will realize that such high temperature hydrogen generators are generally not suitable for use with portable electronic devices.
- Endothermic Hydrogen Generators
- A variety of endothermic hydrogen generators are known, any of which may be used in the methods and apparatus disclosed herein. In certain embodiments of the invention, endothermic hydrogen generators utilize metal hydrides that can reversibly adsorb or release hydrogen gas. Hydrogen uptake by such metal hydrides is an exothermic process. Hydrogen release is endothermic and can be activated by heating the metal hydride, decreasing the external pressure or irradiating the metal hydride with a laser.
- Metal hydride based hydrogen generators are one of the most commonly used hydrogen generation systems (e.g., U.S. Pat. Nos. 4,211,537; 4,728,580; 4,667,185; 6,165,643). Endothermic hydrogen generation using metal hydride or metal alloy hydrides is well known (U.S. Pat. Nos. 4,302,217; 4,537,761; 4,570,446; 4,599,867; 5,360,461; 5,797,269; 5,962,155; 5,987,895; 6,143,052; 6,194,092; 6,267,229). Any such hydride based endothermic hydrogen generator may be used in the methods and apparatus disclosed herein.
- In another exemplary embodiment of the invention, an endothermic hydrogen generator comprises carbon nanotube hydrogen storage systems (e.g., Dillon et al., “Carbon Nanotube Materials for Hydrogen Storage,” Proceedings of the 2001 DOE Hydrogen Program Review, http://www.eren.doe.gov/hydrogen/pdfs/30535am.pdf). In this system, single-walled carbon nanotubes can reportedly store up to 7 weight percent of hydrogen gas. It is suggested that semi-conducting carbon nanotubes are capable of storing more hydrogen than metallic nanotubes. Methods for preparing carbon nanotubes are well known (e.g., U.S. Pat. Nos. 6,258,401; 6,283,812; 6,297,592). Carbon nanotubes may also be obtained from commercial sources, such as CarboLex (Lexington, Ky.), NanoLab (Watertown, Mass.), Materials and Electrochemical Research (Tucson, Ariz. or Carbon Nano Technologies Inc. (Houston, Tex.). Methods of adsorption and desorption of hydrogen from carbon nanotubes, suitable for use in the presently disclosed methods and apparatus, are disclosed in Dillon et al. (2001).
- In alternative embodiments of the invention, endothermic hydrogen generators may comprise tanks containing compressed hydrogen gas or liquid hydrogen. Expansion of compressed gas or conversion of liquid hydrogen to gaseous hydrogen are endothermic processes that may be used in the disclosed methods and apparatus. In another alternative embodiment of the invention, an endothermic hydrogen generator is disclosed in U.S. Pat. No. 5,601,937, discussed above in connection with hydrocarbon reformation. Catalytic decomposition of methanol into hydrogen and carbon monoxide is also an endothermic process
- Control Mechanisms
- In certain embodiments of the invention, the rate of exothermic and/or endothermic hydrogen generation may be regulated by various control mechanisms. A variety of mechanisms for regulating hydrogen generators are known (e.g., U.S. Pat. Nos. 4,211,537; 4,302,217; 5,372,617; 5,702,491; 5,797,269; 5,987,895; 6,267,792). Any known control mechanism for regulating hydrogen generation may be used in the disclosed methods and apparatus.
- Such control mechanisms may be either active or passive in nature. For example, a requirement for electrical power, such as turning on an electrical device powered by a fuel cell, could serve as a signal to initiate exposure of a platinum catalyst to an aqueous borohydride solution, initiating exothermic hydrogen production. The amount of hydrogen and electrical power generated will be directly correclated to the surface area of the catalyst exposed to the borohydride solution. Heat released by the exothermic process could be passively transferred to an endothermic hydrogen generator, such as a metal hydride. In some embodiments of the invention, heat transfer may be facilitated by incorporation of heat transfer mechanisms, such as radiative fins, liquid filled tubes or a heat conductive material such as aluminum or copper. Absorption of heat by a metal hydride would initiate endothermic hydrogen production. In certain embodiments-of the invention, the rate of endothermic hydrogen production may be passively controlled by the rate of heat generation from exothermic hydrogen production. In some alternative embodiments of the invention, an external heat source, such as a resistive electrical heater, may be used. In other alternative embodiments of the invention, waste heat generated by a fuel cell, such as a PEM fuel cell, could be transferred to an endothermic hydrogen generator to provide an additional source of heat.
- In certain embodiments of the invention, the electrical power generated by a hydrogen fuel cell may be supplemented by an additional battery. This additional source of electrical power could be used, for example, to assist in the initiation of hydrogen production, such as by powering a heater to facilitate endothermic hydrogen production, by opening or closing valves or covers to regulate exposure of a borohydride solution to a catalyst or to regulate the amount of water or water vapor added to a chemical hydride.
- In some embodiments of the invention, the control mechanism for regulating the amount of catalyst exposed to borohydride solution may receive input from one or more temperature sensors, such as a thermistor, that monitors the temperature of the exothermic hydrogen generator, the endothermic hydrogen generator or the fuel cell compartment. The control mechanism may incorporate a microprocessor, microcontroller or other control mechanism that prevents the temperature from exceeding predetermined limits.
- In other embodiments of the invention, a more active mechanism of regulating hydrogen generation may be used. Such a mechanism, for example, could control the rates of both exothermic and endothermic hydrogen production to more precisely control the overall temperature of the hydrogen storage system, fuel cell or electronic device. In certain embodiments of the invention, the rates of endothermic and exothermic hydrogen generation may be balanced to provide an overall thermally neutral hydrogen generation, or even a net endothermic hydrogen generation. In other embodiments of the invention, a microcontroller or other control mechanism could regulate the rates of endothermic and/or exothermic hydrogen generation to maintain a selected temperature of the hydrogen storage system, fuel cell and/or electronic device. Alternatively, the temperature of the hydrogen storage system could be controlled to correspond to the ambient temperature of the environment.
- In various embodiments of the invention, any accessory mechanisms, devices or components appropriate for control of the hydrogen generators, including without limitation valves, pumps, covers, relief valves, sensors, thermistors, microcontrollers, controllers, microprocessors, displays, readouts, manifolds, etc. may be used in the disclosed methods and apparatus.
- The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered to function well in the practice of the disclosed embodiments of the invention. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments of the invention which are disclosed and still obtain a like or similar result within the scope of the claimed subject matter.
-
FIG. 1 discloses an exemplary embodiment of the invention comprising a thermally efficienthydrogen storage system 100. Thesystem 100 comprises afirst compartment 110 containing afirst hydrogen generator 120. Inside thefirst compartment 110 is asecond compartment 130 containing asecond hydrogen generator 140. Both the first and second compartments (110, 130) are connected through ports (160, 170) to an external device, such as a fuel cell. The ports (160, 170) allow for the passage of hydrogen gas from the hydrogen generators (120, 140) to the external device. - In various embodiments of the invention, the ports (160, 170) may incorporate filters. In exemplary embodiments of the invention, porous metal filters or porous polytetrafluoroethylene films may be used. However, any filter that allows the free passage of hydrogen gas, while preventing movement of the components of the hydrogen generators (120, 140), may be used.
- In certain embodiments of the invention, the movement of hydrogen may be regulated by various valves, pumps or other control mechanisms, as disclosed above. In other embodiments of the invention, the rates of hydrogen generation by the first (120) and/or second (140) hydrogen generators may also be regulated by various control mechanisms, as disclosed above.
- In certain embodiments of the invention, the hydrogen generators (120, 140) may be reversible. That is, depending on the hydrogen generators (120, 140) used, it may be possible to recharge the
hydrogen storage system 100 with hydrogen after thesystem 100 has been discharged. In this case, the ports (160, 170) may serve as hydrogen recharge ports, allowing uptake of hydrogen into the first and second compartments (110, 130). - In the exemplary embodiment shown in
FIG. 1 , thefirst compartment 110 contains anendothermic hydrogen generator 120, comprising a metal hydride that has been charged with hydrogen gas. In this embodiment, thesecond compartment 130 contains anexothermic hydrogen generator 140, comprising an aqueous solution of sodium borohydride and a catalyst, for example, platinum. As a result of exothermic hydrogen generation in thesecond compartment 130, heat is produced and is transferred to thefirst compartment 110. This transfer ofheat 150 results in the release of hydrogen from themetal hydride 120, which requires input of heat in order to produce hydrogen. Since the heat produced by theexothermic hydrogen generator 140 is largely absorbed by the operation of theendothermic hydrogen generator 120, the net release ofheat 180 by thehydrogen storage system 100 is low. In some embodiments of the invention, the rates of exothermic and/or endothermic hydrogen production may be controlled so that thehydrogen storage system 100 is thermally neutral. In this case, heat released 150 by theexothermic hydrogen generator 140 is balanced by heat absorbed by theendothermic hydrogen generator 120. In certain embodiments of the invention, thefirst compartment 110 may be enclosed by a container composed of materials of low thermal conductivity to increase the efficiency of heat absorption by theendothermic hydrogen generator 120. Such materials are well known in the art. - In some embodiments of the invention, the efficiency of heat transfer between the first 110 and second 130 compartments may be increased by using any known method of heat transfer. For example, the container enclosing the inner,
second compartment 130 may be comprised in whole or in part of a substance with a relatively high heat conductance, such as copper or aluminum. Heat transfer may be increased by the addition of metal fins extending into the first 110 and/orsecond compartment 130. In other exemplary embodiments of the invention, tubes filled with a heat conducting liquid may extend through the first 110 and/orsecond compartment 130. The tubes may or may not have fins or other projections attached to increase the efficiency of heat transfer. Various methods and designs to increase heat transfer in hydrogen generators are known (see, e.g., U.S. Pat. Nos. 4,211,537; 4,302,217; 4,570,446; 4,599,867; 5,962,155; 6,194,092; 6,267,229), any of which may be used in the methods and apparatus disclosed herein. -
FIG. 2 illustrates another exemplary embodiment of the invention. A portableelectronic device 260 comprises at least oneexothermic hydrogen generator 210 and at least oneendothermic hydrogen generator 220. The exothermic 210 and endothermic 220 hydrogen generators are operably coupled to afuel cell 230, to provide hydrogen to thefuel cell 230. Thefuel cell 230, may be anyfuel cell 230 known in the art that utilizes hydrogen to produce electrical power. Certain embodiments of the invention comprise afuel cell 230 designed to operate at near ambient temperature. Thefuel cell 230 comprises positive 240 and negative 250 terminals. Thefuel cell 230 is operably coupled to the portableelectronic device 260 to provide electrical power to the portableelectronic device 260. - All of the METHODS and APPARATUS disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. It will be apparent to those of skill in the art that variations may be applied to the METHODS and APPARATUS and in the elements or in the sequence of elements of the methods described herein within the scope of the claimed subject matter. More specifically, it will be apparent that certain agents that are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the claimed subject matter.
Claims (21)
1-23. (canceled)
24. An apparatus comprising:
a first container enclosing an exothermic hydrogen generator;
a second container enclosing an endothermic hydrogen generator, wherein the endothermic hydrogen generator is to absorb heat released by the exothermic hydrogen generator, and wherein the first container is inside the second container;
a substance having a low thermal conductivity enclosing the first container;
a substance having a high heat conductance enclosing the second container;
one or more ports to allow hydrogen to be removed from the first and second containers.
25. The apparatus of claim 24 , further comprising a conductive fin extending into either the first container, the second container, or both the first and the second containers.
26. The apparatus of claim 24 , further comprising a tube to include a heat conducting liquid extending through the first container, the second container, or both the first and the second containers.
27. An apparatus comprising:
a first container enclosing an exothermic hydrogen generator;
a second container coupled with the first container, the second container enclosing an endothermic hydrogen generator,
wherein the endothermic hydrogen generator is to absorb heat released by the exothermic hydrogen generator.
28. The apparatus of claim 27 , wherein the first container is inside the second container.
29. The apparatus of claim 28 , further comprising a substance enclosing the first container having a high heat conductance.
30. The apparatus of claim 29 , further comprising a material enclosing the first container having a low thermal conductivity.
31. The apparatus of claim 27 , further comprising a conductive fin extending into either the first container, the second container, or both the first and the second containers.
32. The apparatus of claim 27 , further comprising a tube to include a heat conducting liquid extending through the first container, the second container, or both the first and the second containers.
33. The apparatus of claim 27 , wherein the exothermic hydrogen generator is selected from the group consisting of a borohydride solution exposed to a catalyst, a solid lithium aluminum tetrahydride, a hydride exposed to water, and combinations thereof.
34. The apparatus of claim 33 , wherein the endothermic hydrogen generator is selected from the group consisting of one or more metal hydrides, one or more metal alloy hydrides, a carbon nanotube system, a compressed hydrogen gas, a liquid hydrogen, and combinations thereof.
35. The apparatus of claim 34:
wherein the exothermic hydrogen generator comprises an aqueous solution of sodium borohydride and a catalyst; and
wherein the endothermic hydrogen generator comprises one or more metal hydrides.
36. The apparatus of claim 27 , wherein heat released by the exothermic hydrogen generator is approximately balanced by heat absorbed by the endothermic hydrogen generator.
37. The apparatus of claim 27 , further comprising an electrical heater to heat the endothermic hydrogen generator.
38. An apparatus comprising:
a first compartment containing an exothermic hydrogen generator;
a second compartment containing an endothermic hydrogen generator,
wherein the endothermic hydrogen generator is to absorb heat released by the exothermic hydrogen generator.
39. The apparatus of claim 38 , wherein a compartment is inside another compartment.
40. The apparatus of claim 38 , further comprising a conductive fin to transfer heat from the first compartment to the second compartment.
41. The apparatus of claim 38 , further comprising a liquid filled tube to conduct heat from the first compartment to the second compartment.
42. The apparatus of claim 38 , further comprising a substance between the exothermic hydrogen generator and the endothermic hydrogen generator having a high heat conductance.
43. The apparatus of claim 38 , wherein the endothermic hydrogen generator comprises one or more metal hydrides.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/399,920 US20060188762A1 (en) | 2002-02-28 | 2006-04-07 | Thermally efficient hydrogen storage system |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/086,904 US7108933B2 (en) | 2002-02-28 | 2002-02-28 | Thermally efficient hydrogen storage system |
US11/399,920 US20060188762A1 (en) | 2002-02-28 | 2006-04-07 | Thermally efficient hydrogen storage system |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/086,904 Division US7108933B2 (en) | 2002-02-28 | 2002-02-28 | Thermally efficient hydrogen storage system |
Publications (1)
Publication Number | Publication Date |
---|---|
US20060188762A1 true US20060188762A1 (en) | 2006-08-24 |
Family
ID=27753865
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/086,904 Expired - Fee Related US7108933B2 (en) | 2002-02-28 | 2002-02-28 | Thermally efficient hydrogen storage system |
US11/399,920 Abandoned US20060188762A1 (en) | 2002-02-28 | 2006-04-07 | Thermally efficient hydrogen storage system |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/086,904 Expired - Fee Related US7108933B2 (en) | 2002-02-28 | 2002-02-28 | Thermally efficient hydrogen storage system |
Country Status (1)
Country | Link |
---|---|
US (2) | US7108933B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090110973A1 (en) * | 2007-10-30 | 2009-04-30 | Sang-Jun Kong | Fuel cell system |
US20120328491A1 (en) * | 2007-03-26 | 2012-12-27 | Protonex Technology Corporation | Compositions, devices and methods for hydrogen generation |
Families Citing this family (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080020248A1 (en) * | 2002-05-03 | 2008-01-24 | Ion America Corporation | Hydrocarbon gas carbon nanotube storage media |
US7393369B2 (en) | 2002-06-11 | 2008-07-01 | Trulite, Inc. | Apparatus, system, and method for generating hydrogen |
US6918382B2 (en) * | 2002-08-26 | 2005-07-19 | Energy Conversion Devices, Inc. | Hydrogen powered scooter |
US20070125776A1 (en) * | 2003-02-28 | 2007-06-07 | Towler Gavin P | Solid Fuel Devices for Fuel Cells |
US7169497B2 (en) * | 2003-05-15 | 2007-01-30 | The Gillette Company | Electrochemical cells |
US7556660B2 (en) | 2003-06-11 | 2009-07-07 | James Kevin Shurtleff | Apparatus and system for promoting a substantially complete reaction of an anhydrous hydride reactant |
DE10332438A1 (en) * | 2003-07-16 | 2005-04-14 | Studiengesellschaft Kohle Mbh | Materials encapsulated in porous matrices for reversible hydrogen storage |
GB0317894D0 (en) * | 2003-07-31 | 2003-09-03 | Johnson Matthey Plc | Hydrogen supply system |
EP1814653B1 (en) | 2004-11-12 | 2012-07-18 | Trulite, Inc. | Hydrogen generator cartridge |
US20060201148A1 (en) * | 2004-12-07 | 2006-09-14 | Zabtcioglu Fikret M | Hydraulic-compression power cogeneration system and method |
US8148021B2 (en) | 2005-09-23 | 2012-04-03 | SOCIéTé BIC | Methods and apparatus for refueling reversible hydrogen-storage systems |
US8215342B2 (en) | 2005-09-30 | 2012-07-10 | Societé BIC | Hydrogen supplies and related methods |
EP1829820A1 (en) * | 2006-02-16 | 2007-09-05 | Sociedad española de carburos metalicos, S.A. | Method for obtaining hydrogen |
US20090060833A1 (en) * | 2006-03-15 | 2009-03-05 | Societe Bic | Fuel Compositions for Fuel Cells and Gas Generators Utilizing Same |
DE102006027179A1 (en) * | 2006-06-12 | 2007-12-13 | Bayerische Motoren Werke Ag | Fuel storage device for a motor vehicle operated with hydrogen |
US7648786B2 (en) | 2006-07-27 | 2010-01-19 | Trulite, Inc | System for generating electricity from a chemical hydride |
US7651542B2 (en) | 2006-07-27 | 2010-01-26 | Thulite, Inc | System for generating hydrogen from a chemical hydride |
US20100196199A1 (en) * | 2007-03-01 | 2010-08-05 | Andritz Separation Inc. | System and method for treatment of pathogens in dried sewage sludge |
WO2008118436A1 (en) * | 2007-03-26 | 2008-10-02 | Millennium Cell, Inc. | Techniques for packaging and utilizing solid hydrogen-producing fuel |
US8003073B2 (en) * | 2007-04-16 | 2011-08-23 | Air Products And Chemicals, Inc. | Autothermal hydrogen storage and delivery systems |
US8357214B2 (en) | 2007-04-26 | 2013-01-22 | Trulite, Inc. | Apparatus, system, and method for generating a gas from solid reactant pouches |
EP2181477A4 (en) | 2007-07-25 | 2011-08-03 | Trulite Inc | Apparatus, system, and method to manage the generation and use of hybrid electric power |
KR101042299B1 (en) * | 2007-12-13 | 2011-06-17 | 기아자동차주식회사 | Fuel Cell Automotive Hydrogen Storage System |
US8449757B2 (en) * | 2008-01-04 | 2013-05-28 | Societe Bic | Combined chemistry hydrogen generation system |
US7538006B1 (en) | 2008-05-24 | 2009-05-26 | International Business Machines Corporation | Annular damascene vertical natural capacitor |
US9017436B2 (en) | 2008-08-26 | 2015-04-28 | Dcns | Fuel processing systems with thermally integrated componentry |
US20100055518A1 (en) * | 2008-08-26 | 2010-03-04 | Idatech, Llc | Hydrogen-producing assemblies, fuel cell systems including the same, methods of producing hydrogen gas, and methods of powering an energy-consuming device |
US8492042B2 (en) * | 2009-12-02 | 2013-07-23 | Idatech, Llc | Fuel cell systems and methods for providing power and cooling to an energy-consuming device |
CN102130347B (en) * | 2010-01-15 | 2013-10-16 | 扬光绿能股份有限公司 | Fuel cell fuel cartridge and fuel cartridge operating method |
FR2999169B1 (en) * | 2012-12-12 | 2014-12-26 | Herakles | PYROTECHNIC PROCESS FOR PROVIDING LOW PRESSURIZED HYDROGEN AND AT A TEMPERATURE OF LESS THAN 200 ° C AND DEVICE THEREFOR |
US20140238634A1 (en) * | 2013-02-26 | 2014-08-28 | Battelle Memorial Institute | Reversible metal hydride thermal energy storage systems, devices, and process for high temperature applications |
FR3037942B1 (en) * | 2015-06-26 | 2020-07-24 | Commissariat Energie Atomique | HYDRURATION PROCESS OF AN INTERMETAL COMPOUND AND HYDRURATION DEVICE |
DE102015222695B4 (en) * | 2015-11-17 | 2021-07-22 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Energy system and method for storing and / or providing hydrogen |
KR20170097386A (en) | 2016-02-18 | 2017-08-28 | 현대자동차주식회사 | Solid state hydrogen storage divice |
CN108793071A (en) * | 2018-07-21 | 2018-11-13 | 武汉市能智达科技有限公司 | A kind of no electrical heating quickly starts hydrogen storage material hydrogen production process and its device |
CN110767921B (en) * | 2019-11-07 | 2022-10-11 | 安徽伯华氢能源科技有限公司 | Hydrogen fuel cell system |
Citations (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3607066A (en) * | 1966-08-30 | 1971-09-21 | Varta Ag | Process for the production of hydrogen and oxygen gases |
US4000003A (en) * | 1976-01-02 | 1976-12-28 | The United States Of America As Represented By The Secretary Of The Army | Fuel cell-secondary cell combination |
US4002726A (en) * | 1975-07-16 | 1977-01-11 | The United States Of America As Represented By The United States Energy Research And Development Administration | Method of recycling lithium borate to lithium borohydride through methyl borate |
US4211537A (en) * | 1978-07-24 | 1980-07-08 | Teitel Robert J | Hydrogen supply method |
US4302217A (en) * | 1978-07-24 | 1981-11-24 | Teitel Robert J | Hydrogen supply system |
US4537761A (en) * | 1983-03-14 | 1985-08-27 | Liquid Carbonic Inc. | Hydrogen storage system |
US4570446A (en) * | 1984-05-22 | 1986-02-18 | Mitsui & Co., Ltd. | Fuel tank for hydrogen vehicle and fuel supplying system |
US4599867A (en) * | 1985-01-25 | 1986-07-15 | Retallick William B | Hydrogen storage cell |
US4628010A (en) * | 1985-12-13 | 1986-12-09 | The United States Of America As Represented By The Secretary Of The Navy | Fuel cell with storable gas generator |
US4667185A (en) * | 1985-12-06 | 1987-05-19 | Minnesota Mining And Manufacturing Company | Wireless synchronization system for electronic article surveillance system |
US4667815A (en) * | 1985-01-21 | 1987-05-26 | Mannesmann Aktiengesellschaft | Hydrogen storage |
US4728580A (en) * | 1985-03-29 | 1988-03-01 | The Standard Oil Company | Amorphous metal alloy compositions for reversible hydrogen storage |
US5360461A (en) * | 1993-08-23 | 1994-11-01 | United Technologies Corporation | Polymeric storage bed for hydrogen |
US5372617A (en) * | 1993-05-28 | 1994-12-13 | The Charles Stark Draper Laboratory, Inc. | Hydrogen generation by hydrolysis of hydrides for undersea vehicle fuel cell energy systems |
US5601937A (en) * | 1995-01-25 | 1997-02-11 | Westinghouse Electric Corporation | Hydrocarbon reformer for electrochemical cells |
US5702491A (en) * | 1995-06-07 | 1997-12-30 | Ball Corporation | Portable hydrogen generator |
US5797269A (en) * | 1996-02-23 | 1998-08-25 | Sanyo Electric Co., Ltd. | Hydrogen storage containers |
US5928805A (en) * | 1997-11-20 | 1999-07-27 | Siemens Westinghouse Power Corporation | Cover and startup gas supply system for solid oxide fuel cell generator |
US5962155A (en) * | 1996-01-22 | 1999-10-05 | Matsushita Electric Industrial Co., Ltd. | Fuel cell system |
US6074447A (en) * | 1997-02-21 | 2000-06-13 | University Of Hawaii | Hydrogen storage |
US6074453A (en) * | 1996-10-30 | 2000-06-13 | Iowa State University Research Foundation, Inc. | Ultrafine hydrogen storage powders |
US6143052A (en) * | 1997-07-03 | 2000-11-07 | Kiyokawa Plating Industries, Co., Ltd. | Hydrogen storage material |
US6165643A (en) * | 1997-05-01 | 2000-12-26 | Johnson Matthey Public Limited Company | Hydrogen storage materials |
US6194092B1 (en) * | 1997-11-07 | 2001-02-27 | Matsushita Electric Industrial Co., Ltd. | Fuel cell apparatus |
US6258401B1 (en) * | 1997-01-16 | 2001-07-10 | Robert Joseph Crowley | Optical antenna array for harmonic generation, mixing and signal amplification |
US6267229B1 (en) * | 1996-04-01 | 2001-07-31 | Westinghouse Savannah River Company | Apparatus and methods for storing and releasing hydrogen |
US6267792B1 (en) * | 1998-08-03 | 2001-07-31 | Toyota Jidosha Kabushiki Kaisha | Control apparatus and control method for reformer |
US20010010873A1 (en) * | 1998-09-14 | 2001-08-02 | Frank Thom | Solid oxide fuel cell operating with an excess of fuel |
US6274093B1 (en) * | 1998-08-06 | 2001-08-14 | Ball Aerospace & Technologies Corp. | Self-regulating hydrogen generator |
US6283812B1 (en) * | 1999-01-25 | 2001-09-04 | Agere Systems Guardian Corp. | Process for fabricating article comprising aligned truncated carbon nanotubes |
US6297592B1 (en) * | 2000-08-04 | 2001-10-02 | Lucent Technologies Inc. | Microwave vacuum tube device employing grid-modulated cold cathode source having nanotube emitters |
US6318306B1 (en) * | 1999-04-06 | 2001-11-20 | Nissan Motor Co., Ltd. | Internal combustion engine equipped with fuel reforming system |
US20020071797A1 (en) * | 2000-10-06 | 2002-06-13 | Loffler Daniel G. | Catalytic separator plate reactor and method of catalytic reforming of fuel to hydrogen |
US20030021741A1 (en) * | 2001-04-26 | 2003-01-30 | Robert Childress | Compact fuel processor |
US20030103880A1 (en) * | 2001-08-11 | 2003-06-05 | Bunk Kenneth J. | Fuel processor utilizing heat pipe cooling |
US20040154222A1 (en) * | 2003-02-07 | 2004-08-12 | Burch Steven D. | Fuel processor primary reactor and combustor startup via electrically-heated catalyst |
US20040209137A1 (en) * | 2001-03-27 | 2004-10-21 | Corey John A. | Methods and apparatuses for managing effluent products in a fuel cell system |
US20040209131A1 (en) * | 2001-06-16 | 2004-10-21 | Bolton Leslie William | Process and apparatus for producing hydrogen |
-
2002
- 2002-02-28 US US10/086,904 patent/US7108933B2/en not_active Expired - Fee Related
-
2006
- 2006-04-07 US US11/399,920 patent/US20060188762A1/en not_active Abandoned
Patent Citations (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3607066A (en) * | 1966-08-30 | 1971-09-21 | Varta Ag | Process for the production of hydrogen and oxygen gases |
US4002726A (en) * | 1975-07-16 | 1977-01-11 | The United States Of America As Represented By The United States Energy Research And Development Administration | Method of recycling lithium borate to lithium borohydride through methyl borate |
US4000003A (en) * | 1976-01-02 | 1976-12-28 | The United States Of America As Represented By The Secretary Of The Army | Fuel cell-secondary cell combination |
US4211537A (en) * | 1978-07-24 | 1980-07-08 | Teitel Robert J | Hydrogen supply method |
US4302217A (en) * | 1978-07-24 | 1981-11-24 | Teitel Robert J | Hydrogen supply system |
US4537761A (en) * | 1983-03-14 | 1985-08-27 | Liquid Carbonic Inc. | Hydrogen storage system |
US4570446A (en) * | 1984-05-22 | 1986-02-18 | Mitsui & Co., Ltd. | Fuel tank for hydrogen vehicle and fuel supplying system |
US4667815A (en) * | 1985-01-21 | 1987-05-26 | Mannesmann Aktiengesellschaft | Hydrogen storage |
US4599867A (en) * | 1985-01-25 | 1986-07-15 | Retallick William B | Hydrogen storage cell |
US4728580A (en) * | 1985-03-29 | 1988-03-01 | The Standard Oil Company | Amorphous metal alloy compositions for reversible hydrogen storage |
US4667185A (en) * | 1985-12-06 | 1987-05-19 | Minnesota Mining And Manufacturing Company | Wireless synchronization system for electronic article surveillance system |
US4628010A (en) * | 1985-12-13 | 1986-12-09 | The United States Of America As Represented By The Secretary Of The Navy | Fuel cell with storable gas generator |
US5372617A (en) * | 1993-05-28 | 1994-12-13 | The Charles Stark Draper Laboratory, Inc. | Hydrogen generation by hydrolysis of hydrides for undersea vehicle fuel cell energy systems |
US5360461A (en) * | 1993-08-23 | 1994-11-01 | United Technologies Corporation | Polymeric storage bed for hydrogen |
US5601937A (en) * | 1995-01-25 | 1997-02-11 | Westinghouse Electric Corporation | Hydrocarbon reformer for electrochemical cells |
US5702491A (en) * | 1995-06-07 | 1997-12-30 | Ball Corporation | Portable hydrogen generator |
US5962155A (en) * | 1996-01-22 | 1999-10-05 | Matsushita Electric Industrial Co., Ltd. | Fuel cell system |
US5797269A (en) * | 1996-02-23 | 1998-08-25 | Sanyo Electric Co., Ltd. | Hydrogen storage containers |
US5987895A (en) * | 1996-02-23 | 1999-11-23 | Sanyo Electric Co., Ltd. | Hydrogen storage containers |
US6267229B1 (en) * | 1996-04-01 | 2001-07-31 | Westinghouse Savannah River Company | Apparatus and methods for storing and releasing hydrogen |
US6074453A (en) * | 1996-10-30 | 2000-06-13 | Iowa State University Research Foundation, Inc. | Ultrafine hydrogen storage powders |
US6258401B1 (en) * | 1997-01-16 | 2001-07-10 | Robert Joseph Crowley | Optical antenna array for harmonic generation, mixing and signal amplification |
US6074447A (en) * | 1997-02-21 | 2000-06-13 | University Of Hawaii | Hydrogen storage |
US6165643A (en) * | 1997-05-01 | 2000-12-26 | Johnson Matthey Public Limited Company | Hydrogen storage materials |
US6143052A (en) * | 1997-07-03 | 2000-11-07 | Kiyokawa Plating Industries, Co., Ltd. | Hydrogen storage material |
US6194092B1 (en) * | 1997-11-07 | 2001-02-27 | Matsushita Electric Industrial Co., Ltd. | Fuel cell apparatus |
US5928805A (en) * | 1997-11-20 | 1999-07-27 | Siemens Westinghouse Power Corporation | Cover and startup gas supply system for solid oxide fuel cell generator |
US6267792B1 (en) * | 1998-08-03 | 2001-07-31 | Toyota Jidosha Kabushiki Kaisha | Control apparatus and control method for reformer |
US6274093B1 (en) * | 1998-08-06 | 2001-08-14 | Ball Aerospace & Technologies Corp. | Self-regulating hydrogen generator |
US20010010873A1 (en) * | 1998-09-14 | 2001-08-02 | Frank Thom | Solid oxide fuel cell operating with an excess of fuel |
US6283812B1 (en) * | 1999-01-25 | 2001-09-04 | Agere Systems Guardian Corp. | Process for fabricating article comprising aligned truncated carbon nanotubes |
US6318306B1 (en) * | 1999-04-06 | 2001-11-20 | Nissan Motor Co., Ltd. | Internal combustion engine equipped with fuel reforming system |
US6297592B1 (en) * | 2000-08-04 | 2001-10-02 | Lucent Technologies Inc. | Microwave vacuum tube device employing grid-modulated cold cathode source having nanotube emitters |
US20020071797A1 (en) * | 2000-10-06 | 2002-06-13 | Loffler Daniel G. | Catalytic separator plate reactor and method of catalytic reforming of fuel to hydrogen |
US20040209137A1 (en) * | 2001-03-27 | 2004-10-21 | Corey John A. | Methods and apparatuses for managing effluent products in a fuel cell system |
US20030021741A1 (en) * | 2001-04-26 | 2003-01-30 | Robert Childress | Compact fuel processor |
US20050000160A1 (en) * | 2001-04-26 | 2005-01-06 | Texaco Inc. | Compact fuel processor |
US20040209131A1 (en) * | 2001-06-16 | 2004-10-21 | Bolton Leslie William | Process and apparatus for producing hydrogen |
US20030103880A1 (en) * | 2001-08-11 | 2003-06-05 | Bunk Kenneth J. | Fuel processor utilizing heat pipe cooling |
US20040154222A1 (en) * | 2003-02-07 | 2004-08-12 | Burch Steven D. | Fuel processor primary reactor and combustor startup via electrically-heated catalyst |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120328491A1 (en) * | 2007-03-26 | 2012-12-27 | Protonex Technology Corporation | Compositions, devices and methods for hydrogen generation |
US9061910B2 (en) * | 2007-03-26 | 2015-06-23 | Protonex Technolog Corporation | Compositions, devices and methods for hydrogen generation |
US20090110973A1 (en) * | 2007-10-30 | 2009-04-30 | Sang-Jun Kong | Fuel cell system |
US8263271B2 (en) * | 2007-10-30 | 2012-09-11 | Samsung Sdi Co., Ltd. | Fuel cell system |
Also Published As
Publication number | Publication date |
---|---|
US20030162059A1 (en) | 2003-08-28 |
US7108933B2 (en) | 2006-09-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7108933B2 (en) | Thermally efficient hydrogen storage system | |
JP4953553B2 (en) | Steam carrier generator | |
CN100449843C (en) | Use of an ammonia storage device in production of energy | |
US9543604B2 (en) | Hydrogen generator | |
EP3379632B1 (en) | High power fuel cell system | |
Kim et al. | Hydrogen generation system using sodium borohydride for operation of a 400 W-scale polymer electrolyte fuel cell stack | |
US8492042B2 (en) | Fuel cell systems and methods for providing power and cooling to an energy-consuming device | |
JP3942983B2 (en) | Thermal self-supporting solid oxide fuel cell system | |
US9844765B2 (en) | Hydrogen gas generator | |
US20140248546A1 (en) | Hydrogen generator for a fuel cell | |
US6686076B2 (en) | Electrochemical conversion system | |
JPS6249703B2 (en) | ||
JP2022060865A (en) | Hydrogen generator | |
EP1273057B1 (en) | Electrochemical conversion system using hydrogen storage materials | |
US9705145B2 (en) | Hydrogen generator | |
Baumert et al. | Hydrogen storage for fuel cell powered underwater vehicles | |
JP2009082810A (en) | Thermal insulation device, fuel cell system, and thermal insulation container cooling method | |
US20150203353A1 (en) | Fuel unit, gas generator and system | |
JP5151345B2 (en) | Fuel container and power generation system |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |