US20030167778A1 - Hydrogen storage in nanostructures with physisorption - Google Patents
Hydrogen storage in nanostructures with physisorption Download PDFInfo
- Publication number
- US20030167778A1 US20030167778A1 US10/404,303 US40430303A US2003167778A1 US 20030167778 A1 US20030167778 A1 US 20030167778A1 US 40430303 A US40430303 A US 40430303A US 2003167778 A1 US2003167778 A1 US 2003167778A1
- Authority
- US
- United States
- Prior art keywords
- hydrogen
- nanostructured
- storage material
- container
- nanostructured storage
- 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
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 182
- 239000001257 hydrogen Substances 0.000 title claims abstract description 182
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 238000003860 storage Methods 0.000 title claims abstract description 90
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 39
- 238000004375 physisorption Methods 0.000 title claims abstract description 18
- 239000011232 storage material Substances 0.000 claims abstract description 122
- 239000000126 substance Substances 0.000 claims abstract description 56
- 238000001816 cooling Methods 0.000 claims abstract description 39
- 238000003795 desorption Methods 0.000 claims abstract description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 26
- 229910052796 boron Inorganic materials 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000002091 nanocage Substances 0.000 claims description 13
- 229910052790 beryllium Inorganic materials 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- -1 Al2S3 Inorganic materials 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000002064 nanoplatelet Substances 0.000 claims description 8
- 239000002070 nanowire Substances 0.000 claims description 8
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000002121 nanofiber Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 230000003993 interaction Effects 0.000 claims description 6
- 239000002048 multi walled nanotube Substances 0.000 claims description 6
- 239000002073 nanorod Substances 0.000 claims description 6
- 239000002109 single walled nanotube Substances 0.000 claims description 6
- 229910020073 MgB2 Inorganic materials 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 239000002072 nanorope Substances 0.000 claims description 5
- 229910016384 Al4C3 Inorganic materials 0.000 claims description 4
- 229910019752 Mg2Si Inorganic materials 0.000 claims description 4
- 229910020056 Mg3N2 Inorganic materials 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- ZLCCLBKPLLUIJC-UHFFFAOYSA-L disodium tetrasulfane-1,4-diide Chemical compound [Na+].[Na+].[S-]SS[S-] ZLCCLBKPLLUIJC-UHFFFAOYSA-L 0.000 claims description 4
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 3
- 229910001216 Li2S Inorganic materials 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 229910003472 fullerene Inorganic materials 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000012229 microporous material Substances 0.000 claims description 2
- 239000012212 insulator Substances 0.000 claims 5
- 239000002116 nanohorn Substances 0.000 claims 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 230000000737 periodic effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 17
- 238000001179 sorption measurement Methods 0.000 description 17
- 239000002071 nanotube Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000001307 helium Substances 0.000 description 8
- 229910052734 helium Inorganic materials 0.000 description 8
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 8
- 229910052582 BN Inorganic materials 0.000 description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- 239000013590 bulk material Substances 0.000 description 6
- 239000002156 adsorbate Substances 0.000 description 5
- 239000002717 carbon nanostructure Substances 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000002079 double walled nanotube Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000010399 physical interaction Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 229910019884 NaxSy Inorganic materials 0.000 description 1
- 206010039203 Road traffic accident Diseases 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000036963 noncompetitive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007725 thermal activation 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
- C01B3/0005—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
- C01B3/001—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 characterised by the uptaking medium; Treatment thereof
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/902—Specified use of nanostructure
- Y10S977/932—Specified use of nanostructure for electronic or optoelectronic application
- Y10S977/948—Energy storage/generating using nanostructure, e.g. fuel cell, battery
Definitions
- the invention relates to hydrogen storage systems, more particularly to the storage of hydrogen in systems that include nanostructures of combinations of light elements.
- Hydrogen storage is the key unsolved problem of producing fuel cells for hydrogen-powered automobiles or portable energy devices.
- storing hydrogen in large quantities safely and in a light container has proved prohibitively difficult so far.
- Hydrogen can be stored in carbon nanostructures, such as graphite and carbon nanofibers, according to the papers of A. Dillon et al. in Nature, vol. 386, p. 377 (1997), A. Chambers et al. in J. Phys. Chem. B vol. 102, p. 3378 (1998), and E. Poirier et al. in Int. J. of Hydrogen Energy, vol. 26, p. 831 (2001), and according to U.S. Pat. No. 5,653,951: “Storage of hydrogen in layered nanostructures,” by N. Rodriguez and R. Baker; and U.S. Pat. No. 4,960,450: “Selection and preparation of activated carbon for fuel gas storage,” by J. Schwarz et al. Furthermore, hydrogen storage in Al and Si containing zeolites and microporous materials has been explored previously.
- Nanostructures can be defined as atomic structures that have a spatial extent of less than a few hundred nanometers in one, two, or all three dimensions.
- a class of nanostructures is formed by planar networks, sometimes referred to as layered compounds. Layered compounds are often formed by elements coupled with sp 2 bonds. The origin of the sp 2 bonds will be presented on the example of elements of the second row of the periodic table, including boron, carbon and nitrogen.
- FIG. 1 shows an example of a second row element 4 coupled with sp 2 bonds, or orbitals, 8 to three other elements 12 .
- the s orbital of the second row elements is filled with two electrons, and the p orbitals are partially filled.
- boron has one electron
- carbon has two
- nitrogen has three electrons in the p orbitals.
- the second row elements form chemical bonds, one of the s electrons is promoted into an empty p orbital—for example into the p z orbital in carbon, leaving only one s electron. This one s electron and two of the p electrons first hybridize into three sp 2 hybrid orbitals.
- the three hybridized electrons repel each other, and hence form three sp 2 orbitals 8 as far as possible away from each other.
- An optimal configuration is when the three sp 2 orbitals 8 make 120 degrees with each other, defining a plane. Connecting several second row elements with planar sp 2 orbitals 8 spans the defined plane, thus forming the aforementioned planar networks.
- Possible planar networks of the sp 2 bonded materials include triangular lattices. Large sections of a planar network can be deformed to create various nanostructures. Nanostructures that are based on sp 2 bonded triangular lattices include different classes of nanotubes, nanococoons, nanoropes, nanofibers, nanowires, nanohorns, and nanocages.
- U.S. Pat. No. 5,653,951 considered hydrogen storage in carbon nanostructures, utilizing chemisorption.
- chemisorption binds hydrogen to the carbon nanostructure by forming a chemical bond that is typically quite strong. Therefore, chemisorptive bonds can change the chemical composition and structure of the storage material itself. This is a drawback for storage applications, as the storage system has to be operated cyclically without structural degradation in order to be useful.
- the hydrogen might be recovered from the storage material in an altered chemical form, for example, methane. This again reduces the usefulness of storage materials, which form chemisorptive bonds.
- a hydrogen containing nanostructured storage material where the hydrogen is adsorbed to the nanostructured stoage material by physisorption.
- the nanostructured storage material includes light elements, belonging to the second and third rows of the periodic table. More specifically, the light elements are selected from Be, B, C, N, O, F, Mg, P, S, and Cl.
- the chemical composition of the nanostructured storage material is such that the desorption temperature, at which hydrogen desorbs from the nanostructured storage material, is greater than the liquefaction temperature of nitrogen, 77 K.
- Some chemical compositions that give rise to a desorption temperature in excess of 77 K are: B x C y N z , BN, BC 2 N, MgB 2 , Be 3 N 2 , BeB 2 , B 2 O, B, BeO, AlCl 3 , Al 4 C 3 , AlF 3 , Al 2 O 3 , Al 2 S 3 , Mg 2 Si, Mg 3 N 2 , Li x N y , Li x S y , and Na x S y , where x, y, and z are integers.
- the nanostructured storage material is formed as a layered network of light elements, coupled with covalent sp 2 bonds.
- the layered network can be a triangular lattice, a nanofiber, a nanoplatelet, a single walled nanotube, a multi walled nanotube, a nanocage, a nanococoon, a nanorope, a nanotorus, a nanocoil, a nanorod, a nanowire, and a fullerene.
- the layered network can also have a heterogeneous form, including a combination of the above structures, as well as embodiments where various parts of the network can have different chemical composition.
- a hydrogen storage system includes a container and a nanostructured storage material within the container, wherein the nanostructured storage material includes light elements, and the nanostructured storage material is capable of adsorbing hydrogen by physisorption.
- the nanostructured storage material can be, for example, any of the above-described embodiments.
- the nanostructured storage material can be combined with a hydrogen distribution system to facilitate the efficient flow of hydrogen.
- the hydrogen storage system further includes a cooling system, capable of cooling the nanostructured storage material below the desorption temperature of hydrogen in relation to the nanostructured storage material.
- the cooling system includes a middle container within the container, separated by vacuum, an inner container with the middle container, and liquid nitrogen between the middle container and the inner container.
- the nanostructured storage material is within the inner container.
- Some embodiments contain a heater to control the temperature of the nanostructured storage material.
- FIG. 1 illustrates an element with sp 2 bonds.
- FIG. 2A illustrates a plan view of a honeycomb nanostructured storage material.
- FIG. 2B illustrates a perspective view of a honeycomb nanostructured storage material, displaying the adsorbed hydrogen molecules.
- FIG. 3A illustrates a perspective view of a nanotube structure.
- FIG. 3B illustrates a perspective view of a nanotube structure, displaying the adsorbed hydrogen molecules.
- FIG. 4A illustrates a perspective view of a nanocage structure.
- FIG. 4B illustrates a perspective view of a nanocage structure, displaying the adsorbed hydrogen molecules.
- FIG. 5 illustrates the sorption and desorption curves of hydrogen in relation to a nanostructured storage material.
- FIG. 6 illustrates a cooled hydrogen storage system
- FIG. 7 illustrates the temperature dependence of the hydrogen storage capacity in nanostructured storage materials.
- FIGS. 2A and 2B illustrate an embodiment for storing hydrogen in an sp 2 bonded nanostructured storage material 10 with a triangular lattice that has a flat planar network.
- FIG. 2A shows the plan view of nanostructured storage material 10 with a triangular lattice structure, without the hydrogen molecules.
- the chemical composition of nanostructured storage material 10 is of the AB type, an example of which is boron nitride.
- Light elements 16 and light elements 20 of nanostructured storage material 10 are shown with bigger and smaller empty circles, respectively.
- Light elements 16 and 20 are coupled with sp 2 bonds 24 .
- suitable light elements see below.
- FIG. 2B shows a perspective view of the triangular lattice, wherein hydrogen molecules 28 are shown in their bonding position.
- hydrogen molecules 28 are positioned over the center of the hexagons of the triangular lattice, in other embodiments hydrogen molecules 28 are positioned over a bond or over an atom of the lattice.
- there is one energetically favored position for hydrogen molecules 28 in other embodiments there are several substantially equivalent positions.
- the orientation of hydrogen molecules 28 can be parallel to the local plane of the triangular lattice, in other embodiments the orientation can be perpendicular, or it can make some other angle with the local plane of the triangular lattice.
- the adsorption properties of hydrogen to nanostructured storage material 10 depend on the nature of sp 2 bonds 24 . In some embodiments this property is used, when the adsorption properties of hydrogen to nanostructured storage material 10 are improved by modifying sp 2 bonds 24 .
- Embodiments with modified sp 2 bonds 24 are described, for example, in U.S. patent application entitled: “Increasing Hydrogen Adsorption For Hydrogen Storage In Nanostructured Materials By Modifying sp 2 Covalent Bonds” by Young-Kyun Kwon, Seung-Hoon Jhi, Keith Bradley, Philip G. Collins, Jean-Christophe P. Gabriel, and George Grüner.
- sp 2 bonds 24 are modified, for example, by forming non-planar structures, by introducing various defects, and by introducing different elements into nanostructured storage material 10 .
- the so far passive additional p electron may hybridize to a small degree with the elections, which formed the sp 2 configuration. Therefore, in these embodiments sp 2 bond 24 may acquire a small sp 3 character.
- the covalent bonds of nanostructured storage material 10 may be only substantially sp 2 bonds.
- FIGS. 3A and 32B illustrate some embodiment for storing hydrogen in an sp 2 bonded nanostructured storage material 10 with a planar triangular lattice that has been deformed into a tubular structure, or nanotube.
- FIG. 3A shows a perspective view of the nanotube without the hydrogen molecules, where the chemical composition of nanostructured storage material 10 is of the AB type, an example of which is boron nitride.
- Light elements 16 and light elements 20 of nanostructured storage material 10 are shown with bigger and smaller empty circles, respectively.
- Light elements 16 and 20 are coupled with sp 2 bonds 24 .
- FIG. 3B shows a perspective view of the nanotube, wherein hydrogen molecules 28 are shown in their bonding position.
- hydrogen molecules 28 are positioned over the center of the hexagons of the triangular lattice, in other embodiments hydrogen molecules 28 are positioned over a bond or over an atom of the triangular lattice.
- there is one energetically favored position for hydrogen molecules 28 in other embodiments there are several substantially equivalent positions.
- the orientation of hydrogen molecules 28 can be parallel to the local plane of the triangular lattice, in other embodiments the orientation can be perpendicular, or it can make some other angle with the local plane of the triangular lattice.
- FIGS. 4A and 4B illustrate some embodiment for storing hydrogen in an sp 2 bonded nanostructured storage material 10 with a planar triangular lattice that has been deformed into a cage structure, or nanocage.
- FIG. 4A shows a perspective view of the nanocage without the hydrogen, where the chemical composition of nanostructured storage material 10 is of the AB type, an example of which is boron nitride.
- Light elements 16 and light elements 20 of nanostructured storage material 10 are shown with bigger and smaller empty circles, respectively.
- Light elements 16 and 20 are coupled with sp 2 bonds 24 .
- FIG. 4B shows a perspective view of the nanocage, wherein hydrogen molecules 28 are shown in their bonding position.
- hydrogen molecules 28 are positioned over the center of the hexagons of the triangular lattice, in other embodiments hydrogen molecules 28 are positioned over a bond or over an atom of the triangular lattice.
- there is one energetically favored position for hydrogen molecules 28 in other embodiments there are several substantially equivalent positions.
- the orientation of hydrogen molecules 28 can be parallel to the local plane of the triangular lattice, in other embodiments the orientation can be perpendicular, or it can make some other angle with the local plane of the triangular lattice.
- hydrogen can be stored in other forms of nanostructured storage material 10 .
- a non-exhaustive list of possible forms of nanostructured storage material 10 includes:
- nanofibers of the following kinds turbostatic, highly oriented, twisted, straight, curled and rigid;
- nanotubes of the following kinds single walled, double walled, multi walled, with zig-zag chirality, or a mixture of chiralities, twisted, straight, bent, kinked, curled, flattened, and round;
- thin nanoplatelets thick nanoplatelets, intercalated nanoplatelets, with thickness of about 0.3 nm to about 100 nm, and lateral size of about 5 nm to about 500 nm.
- Heterogeneous forms include structures, where one part of the structure has a certain chemical composition, within another part of the structure has a different chemical composition.
- An example is a multi walled nanotube, where the chemical composition of the different walls can be different from each other.
- Heterogeneous forms also include different forms of nanostructured storage material 10 , where more than one of the above listed forms are joined into a larger irregular structure. Finally, all above d materials can have cracks, dislocations, branches or other imperfections.
- embodiments of the present invention include nanostructured storage material 10 composed of light elements.
- Suitable light elements include elements of the second and third rows of the periodic table: Be, B, C, N, O, F, Mg, P, S, and Cl.
- the storage efficiency of nanostructured storage material 10 can be enhanced by combining the listed suitable light elements. While Al and Si containing nanostructures, such as zeolites, have been explored before for storage purposes, in some embodiments of the invention Al and Si can be combined with the above light elements.
- Some embodiments can contain elements from other rows of the periodic table as well. Some of these elements can be introduced deliberately to enhance a desired property. Other elements may be a residue from the production process, for example, a catalyst. Therefore, it is understood that embodiments of the invention may contain heavier elements in some concentration.
- Some embodiments of the invention include B x C y N z , where x, y, and z are small integers. Making of this material is described, for example, in “Pyrolytically Grown Arrays of Highly Aligned B x C y N z Nantubes”, by W. -Q. Han, J. Cumings, and A. Zettl in Applied Physics Letters, vol. 78, p. 2769 (2001), and in U.S. Pat. No. 6,231,980 “B x C y N z nanotubes and nanoparticles,” by M. Cohen and A. Zettl, which publication and patent are hereby incorporated in their entirety by this reference.
- Some embodiments of the invention include BN. Making of this material is described, for example, in “Mass Production of Boron Nitride Double-wall Nanotubes and Nanococoons,” by J. Cumings and A. Zettl in Chemical Physics Letters, vol. 316, p. 211 (2000), hereby incorporated in its entirety by this reference.
- Some embodiments of the invention include BC 2 N. Making of this material is described, for example, in “Synthesis of B x C y N z Nanotubules,” by Z. Weng-Sieh, K. Cherrey, N. G. Chopra et al., in Physical Review B, vol. 51, p. 11229 (1995), hereby incorporated in its entirety by this reference.
- Some embodiments of the invention include MgB 2 .
- Making of this material is described, for example, in “Superconducing MgB 2 Nanowires,” by Y. Wu, B. Messer, and P. Yang in Advanced Materials, vol. 13, p. 1487 (2001), hereby incorporated in its entirety by this reference.
- Some embodiments of the invention include Be 3 N 2 . Making of this material is described, for example, in “Die Struktur Einer Neuen Modbericht von Be 3 N 2 , ” by P. Eckerlin and A. Rabenau in Angewandte Chemie, vol. 304, p. 218 (1960), hereby incorporated in its entirety by this reference.
- Some embodiments of the invention include BeB 2 .
- Making of this material is described, for example, in “Absence of Superconductivity in BeB 2 , ” by I. Felner in Physica C, vol. 353, p. 11 (2001), hereby incorporated in its entirety by this reference.
- Some embodiments of the invention include B 2 O. Making of this material is described, for example, by H. Hall and L. Compton in Inorganic Chemistry, vol. 4, p. 1213 (1965), hereby incorporated in its entirety by this reference.
- Some embodiments of the invention include elemental boron. Making of this material is described, for example, by S. La Placa, P. Roland, and J. Wynne in Chemical Physics Letter vol. 190, p. 163 (1992), hereby incorporated in its entirety by this reference.
- Some embodiments of the invention include standard materials that are listed in the Chemical Abstract Service (CAS) at the web site: www.cas.org: TABLE 1 Chemical composition CAS number BeO 1304-56-9 AlCl 3 7784-13-6 Al 4 C 3 1299-86-1 AlF 3 7784-18-1 Al 2 O 3 1344-28-1 Al 2 S 3 1302-81-4 Mg 2 Si 22831-39-6 Mg 3 N 2 12057-71-5 Li 3 N 26134-62-3 Li 2 S 12136-58-2 Na 2 S 1313-82-2 Na 2 S 4 12034-39-8
- the hydrogen atoms bonds to nanostructured storage material 10 by physisorption. Therefore, the present invention differs from U.S. Pat. No. 5,653,951, which describes an invention, where “ . . . nanostructures of the present invention store hydrogen by chemisorbing molecular hydrogen in the interstices of the nanostructure” (col. 3, 11.40-42).
- chemisorption is a type of adsorption, where an adsorbate is bound to a surface by the transfer of electrons, forming a chemical bond between the adsorbate and atoms of the surface.
- physisorption is a type of adsorption, where an adsorbate is bound to a surface by physical interactions without the transfer of electrons.
- Physical interactions, giving rise to physisorption include, but are not restricted to, van der Waals interactions. Van der Waals interactions are operational when the neutral atoms or molecules of the adsorbate and the surface polarize each other, and the polarized atoms or molecules attract each other at some distance.
- chemisorptive bonds are strong and physisorptive bonds are weak. This difference manifests itself in the kinetics of the dissolution of the bonds, or desorption. Chemisorptive bonds are dissolved by an activated process, i.e., by thermal activation over an activation energy barrier, which is considerable. For this reason dissolution of chemisorbed bonds proceeds slowly and is not adiabatically reversible.
- U.S. Pat. No. 5,653,951 discusses in great detail the irreversible aspects of desorption of that invention.
- the irreversibility of desorption of that invention is illustrated in FIGS. 1A, 1B, 2 B, 3 A, and 3 B by the fact that the sorption and desorption curves do not coincide.
- Such irreversibility is strong evidence for the chemisorptive nature of hydrogen bonding in U.S. Pat. No. 5,653,951.
- FIG. 5 illustrates the coverage fraction, i.e., the fraction of the adsorbent surface, which is covered by hydrogen, as a function of pressure at a fixed temperature.
- the solid sorption curve indicates the results for starting at a low pressure value, for example, 10 ⁇ 3 atm, and measuring the coverage fraction while increasing the pressure.
- the dashed desorption curve indicates the results for starting at a high pressure value, for example, 1 atm, and measuring the coverage fraction while decreasing the pressure.
- the above embodiments can be manufactured by different techniques.
- the two main acts of manufacturing are the making of nanostructured storage material 10 and the subsequent purifying of nanostructured storage material 10 .
- the making of nanostructured storage material 10 starts by providing the bulk material with the desired chemical composition in polycrystalline or micrograined form.
- the bulk material is then loaded into a ball mill.
- the balls of the ball mill can be stainless steel balls or hard ceramic balls, with a diameter of, for example, about 3 mm.
- the material can be milled for an extended period, for example, 24 hours. The milling can take place in air, in vacuum, or in reactive gases.
- the resulting material will contain some nanostructured storage material 10 , which can be separated by subsequent purifying.
- the making of nanostructured storage material 10 starts with providing a bulk material in powder form.
- the bulk material has the desired chemical composition, in others the bulk material contains some of the desired ingredients.
- the powdered bulk material is pressed into a shape, suitable for functioning as an electrode, an example of such a shape being a rod.
- the rod is then used as an electrode to construct an arc chamber.
- the construction of such an arc chamber is described, for example, in “A Mass Production of Boron Nitride Double Wall Nanotubes and Nanocacoons,” by J. Cumings and A. Zettl in Chemical Physics Letters, vol. 316, p. 211 (2000).
- the arc chamber can be filled up with inert gases, for example, helium.
- the arc chamber can be filled up by one or more reactive gas.
- beryllium nitride, Be 3 N 2 could be made in an arc chamber whose electrode contains beryllium and where the chamber contains nitrogen gas.
- Subsequent purifying of nanostructured storage material 10 can be performed by many methods. Some purifying methods are described by A. Dillon et al. in Advanced Materials, vol. 11, p. 1354 (1999), G. Duesberg et al. in Applied Physics A, vol. 67, p. 117 (1998), K. Shelimov et al. in Chemical Physics Letters, vol. 282, p. 429 (1998), J. Tak et al. in Chemical Physics Letters, vol. 344, p. 18 (2001), P. Young et al. in Carbon, vol. 39, p. 655 (2001), which publications are hereby incorporated in their entirety by this reference. Purifying methods are capable of extracting nanostructured storage material 10 of a particular class and form, for example, corresponding to the above list of nanostructured storage materials 10 .
- FIG. 6 illustrates an embodiment of a hydrogen storage system 100 according to the invention.
- An outer container 104 contains vacuum in outer region 108 to insulate the internal parts of hydrogen storage system 100 from the heat of the environment.
- the vacuum in outer region 108 can be controlled through vacuum valve 110 .
- a pump can be coupled to vacuum valve 110 to reduce the pressure in outer region 108 .
- the pressure in outer region 108 is between about 10 9 atm and 10 ⁇ 1 atm, for example, 10 ⁇ 6 atm.
- Middle container 112 contains a cooling substance 116 to provide cooling of hydrogen storage system 100 .
- Cooling substance 116 can be, for example, liquid nitrogen.
- Cooling systems utilizing liquid nitrogen have multiple advantages over systems utilizing liquid helium.
- Liquid nitrogen is much cheaper per liter than liquid helium.
- Nitrogen becomes a liquid at 77 K, whereas helium becomes a liquid at 4.2 K. It requires much less energy to cool a system to a temperature of 77 K, than to a temperature of 4.2 K. It also requires a much simpler, and therefore lighter cooling apparatus to maintain a temperature of 77 K, than to maintain a temperature of 4.2 K.
- Cooling valve 114 is used to control the cooling substance.
- cooling substance 116 can be supplied through cooling valve 114 , and the evaporated excess cooling substance 116 can be released through cooling valve 114 .
- other cooling substances 116 may be utilized.
- Inner container 120 contains nanostructured storage material 10 .
- Nanostructured storage material 10 can be any embodiment described above or a combination thereof. In some embodiments nanostructured storage material 10 substantially fills up inner container 120 . In other embodiments nanostructured storage material 10 is combined with a hydrogen distribution system, which provides paths for the hydrogen to flow efficiently across the volume of nanostructured storage material 10 .
- the hydrogen distribution system can be, for example, a hierarchical network of tubes of varying diameters to facilitate the efficient flow of hydrogen.
- a hydrogen valve 126 is used to control the hydrogen gas.
- Hydrogen storage system 100 can be filled by coupling hydrogen valve 126 to a hydrogen container through a pump.
- FIG. 7 illustrates the hydrogen storage capacity in percents in nanostructured storage material 10 as a function of the temperature.
- the amount of stored hydrogen is normalized with the amount stored at zero temperature.
- the curves refer to pressures of 1 atm, 10 atm, and 100 atm.
- FIG. 7 illustrates that as the temperature is increased from a low value, hydrogen starts the desorption at a relatively well defined desorption temperature T D .
- the value of T D depends on the pressure, as shown.
- the value of T D is about 60 K for carbon nanostructures and higher for boron nitride nanostructures.
- the temperature is given relative to the desorption temperature T D at 1 atm, T D (1 atm).
- the amount of hydrogen adsorbed in a storage material can be characterized by the percentage wise weight increase of the storage system caused by the adsorption of hydrogen, in units of weight %.
- embodiments of the invention store hydrogen in cooled storage systems at temperatures below the desorption temperature, enabling the storage of much larger quantities.
- hydrogen adsorption below the desorption temperature in some embodiments is between about 3 weight % and about 27 weight %, for example, 7.5 weight %.
- Operating hydrogen storage system 100 below the desorption temperature enhances the storage capacity by a factor of 30 or more in comparison to operating the hydrogen storage system 100 at ambient temperatures.
- embodiments of the invention are operated at or above liquid nitrogen temperatures, and thus do not require the use of liquid helium for cooling purposes.
- cooling systems using liquid nitrogen have many advantages over cooling systems using liquid helium.
- Nanostructured storage materials 124 that have a desorption temperature above 77 K.
- the desorption temperature of nanostructured storage material 10 depends on its chemical composition.
- pure carbon nanostructures typically have desorption temperatures below 77 K
- embodiments that use nanostructured storage materials 124 formed from a combination of light elements have desorption temperatures well above 77 K.
- boron nitride has a desorption temperature which is about 30% higher than that of carbon.
- the operation of hydrogen storage system 100 includes filling up the system with hydrogen and recovering stored hydrogen from the system.
- Hydrogen storage system 100 can be filled up by coupling hydrogen valve 126 to a hydrogen container through a pump. Nanostructured storage material 10 is cooled by cooling substance 116 to temperatures below the desorption temperature. When the pressure of the pump is raised to a suitable value, hydrogen from the hydrogen container will be pumped into inner container 120 , where it will adsorb to nanostructured storage material 10 . Suitable pressure values can lie in the range of, for example, about 1 atm to about 20 atm.
- Hydrogen can be recovered from hydrogen storage system 100 by various methods. Some embodiments recover the hydrogen by heating nanostructured storage material 10 with heater 130 .
- Heater 130 can be, for example, a resistor, driven by a current. The longer the current is applied to heater 130 , or the more current is applied to heater 130 , the higher the temperature of nanostructured storage material 10 will rise. As the temperature rises above the desorption temperature, hydrogen will desorb from nanostructured storage material 10 , and can be recovered through hydrogen valve 126 . In some other embodiments simply the leakage heat, leaking into inner container 120 from the outside, can be used to drive the desorption of hydrogen.
Abstract
A hydrogen containing nanostructure is provided, where the hydrogen is adsorbed to the nanostructure by physisorption. The nanostructure includes light elements, selected from the second and third rows of the periodic table. The nanostructure is formed as a layered network of light elements coupled with covalent sp2 bonds. The chemical composition of the nanostructure can be such that the desorption temperature of hydrogen is greater than the liquefaction temperature of nitrogen, 77 K. Further, a hydrogen storage system is provided, including a container and a nanostructured storage material within the container, wherein the nanostructured storage material includes light elements, and the nanostructured storage material is capable of adsorbing hydrogen by physisorption. The hydrogen storage system can include a liquid nitrogen based cooling system, capable of cooling the nanostructured storage material below the desorption temperature of hydrogen. Some embodiments contain a heater to control the temperature of the nanostructured storage material.
Description
- The present application is related to U.S. patent application entitled: “Increasing Hydrogen Adsorption For Hydrogen Storage In Nanostructured Materials By Modifying sp2 Covalent Bonds” by Young-Kyun Kwon, Seung-Hoon Jhi, Keith Bradley, Philip G. Collins, Jean-Christophe P. Gabriel, and George Grüner, attorney docket number M-12324, filed on the same date as the present application and incorporated herein in its entirety by this reference.
- 1. Field of the Invention
- The invention relates to hydrogen storage systems, more particularly to the storage of hydrogen in systems that include nanostructures of combinations of light elements.
- 2. Description of the Related Art
- Hydrogen storage is the key unsolved problem of producing fuel cells for hydrogen-powered automobiles or portable energy devices. In particular, storing hydrogen in large quantities safely and in a light container has proved prohibitively difficult so far.
- Several different techniques have been developed to tackle this problem. In some approaches hydrogen is stored in tanks under high pressure, for example, 300 atm. In other techniques hydrogen is liquefied at temperatures below 20 K with a helium-based cooling system. Both of these techniques pose problems for practical use in automobiles. All of the hydrogen is available for catastrophic release in an accident, raising the risk of explosion or fire. Furthermore, in order to store enough hydrogen to match the range of present day automobiles, the container has to have a volume of at least 50 gallons. Also, both in the high pressure technique and in the helium cooled technique the required containers are heavy, and therefore inefficient for storage. Finally, both techniques also consume a lot of energy for generating the high pressure or for liquefying the hydrogen.
- Some other techniques adsorb hydrogen into solid materials. Several types of materials have been studied in this respect, including metal hydrides and glass microspheres. However, the materials investigated so far all have low hydrogen storage capacity, making them non-competitive with gasoline.
- Hydrogen can be stored in carbon nanostructures, such as graphite and carbon nanofibers, according to the papers of A. Dillon et al. in Nature, vol. 386, p. 377 (1997), A. Chambers et al. in J. Phys. Chem. B vol. 102, p. 3378 (1998), and E. Poirier et al. in Int. J. of Hydrogen Energy, vol. 26, p. 831 (2001), and according to U.S. Pat. No. 5,653,951: “Storage of hydrogen in layered nanostructures,” by N. Rodriguez and R. Baker; and U.S. Pat. No. 4,960,450: “Selection and preparation of activated carbon for fuel gas storage,” by J. Schwarz et al. Furthermore, hydrogen storage in Al and Si containing zeolites and microporous materials has been explored previously.
- Nanostructures can be defined as atomic structures that have a spatial extent of less than a few hundred nanometers in one, two, or all three dimensions. A class of nanostructures is formed by planar networks, sometimes referred to as layered compounds. Layered compounds are often formed by elements coupled with sp2 bonds. The origin of the sp2 bonds will be presented on the example of elements of the second row of the periodic table, including boron, carbon and nitrogen.
- FIG. 1 shows an example of a
second row element 4 coupled with sp2 bonds, or orbitals, 8 to threeother elements 12. The s orbital of the second row elements is filled with two electrons, and the p orbitals are partially filled. For example, boron has one electron, carbon has two, and nitrogen has three electrons in the p orbitals. When the second row elements form chemical bonds, one of the s electrons is promoted into an empty p orbital—for example into the pz orbital in carbon, leaving only one s electron. This one s electron and two of the p electrons first hybridize into three sp2 hybrid orbitals. The remaining p electrons—none in boron, one in carbon, and two in nitrogen—occupy an orbit that does not participate in the bonding. The three hybridized electrons repel each other, and hence form three sp2 orbitals 8 as far as possible away from each other. An optimal configuration is when the three sp2 orbitals 8 make 120 degrees with each other, defining a plane. Connecting several second row elements with planar sp2 orbitals 8 spans the defined plane, thus forming the aforementioned planar networks. - Possible planar networks of the sp2 bonded materials include triangular lattices. Large sections of a planar network can be deformed to create various nanostructures. Nanostructures that are based on sp2 bonded triangular lattices include different classes of nanotubes, nanococoons, nanoropes, nanofibers, nanowires, nanohorns, and nanocages.
- Storing hydrogen in sp2 bonded nanostructures has the following advantages. Hydrogen, adsorbed to the nanostructures, desorbs over a range of temperatures, and thus it is not available for catastrophic release, for example, in case of an automobile accident. Furthermore, because of their large surface area, nanostructures are capable of adsorbing very large quantities of hydrogen, giving rise to a much higher weight % storage efficiency than the aforementioned high pressure and cooling techniques.
- However, the above works have the following disadvantages. Typically they considered hydrogen storage at ambient temperatures, where the storage capacity fell far short of the theoretical value, making those works economically non-viable. Also, the works that considered storage at other temperatures reported insufficient storage efficiencies.
- In particular, U.S. Pat. No. 5,653,951 considered hydrogen storage in carbon nanostructures, utilizing chemisorption. As described below in detail, chemisorption binds hydrogen to the carbon nanostructure by forming a chemical bond that is typically quite strong. Therefore, chemisorptive bonds can change the chemical composition and structure of the storage material itself. This is a drawback for storage applications, as the storage system has to be operated cyclically without structural degradation in order to be useful.
- Also, because of the formation of chemical bonds, the hydrogen might be recovered from the storage material in an altered chemical form, for example, methane. This again reduces the usefulness of storage materials, which form chemisorptive bonds.
- Therefore, there is a need for hydrogen storage systems that contain sp2 bonded nanostructures, wherein the chemical composition of the nanostructure is selected to ensure high storage efficiency, the storage system operates at technically advantageous temperatures, and in particular wherein the mechanism of hydrogen adsorption is not chemisorption.
- In accordance with the invention, a hydrogen containing nanostructured storage material is provided, where the hydrogen is adsorbed to the nanostructured stoage material by physisorption. The nanostructured storage material includes light elements, belonging to the second and third rows of the periodic table. More specifically, the light elements are selected from Be, B, C, N, O, F, Mg, P, S, and Cl. The chemical composition of the nanostructured storage material is such that the desorption temperature, at which hydrogen desorbs from the nanostructured storage material, is greater than the liquefaction temperature of nitrogen, 77 K. Some chemical compositions that give rise to a desorption temperature in excess of 77 K are: BxCyNz, BN, BC2N, MgB2, Be3N2, BeB2, B2O, B, BeO, AlCl3, Al4C3, AlF3, Al2O3, Al2S3, Mg2Si, Mg3N2, LixNy, LixSy, and NaxSy, where x, y, and z are integers.
- The nanostructured storage material is formed as a layered network of light elements, coupled with covalent sp2 bonds. The layered network can be a triangular lattice, a nanofiber, a nanoplatelet, a single walled nanotube, a multi walled nanotube, a nanocage, a nanococoon, a nanorope, a nanotorus, a nanocoil, a nanorod, a nanowire, and a fullerene. The layered network can also have a heterogeneous form, including a combination of the above structures, as well as embodiments where various parts of the network can have different chemical composition.
- According to another embodiment of the invention, a hydrogen storage system is provided. The hydrogen storage system includes a container and a nanostructured storage material within the container, wherein the nanostructured storage material includes light elements, and the nanostructured storage material is capable of adsorbing hydrogen by physisorption. The nanostructured storage material can be, for example, any of the above-described embodiments. The nanostructured storage material can be combined with a hydrogen distribution system to facilitate the efficient flow of hydrogen.
- In some embodiments the hydrogen storage system further includes a cooling system, capable of cooling the nanostructured storage material below the desorption temperature of hydrogen in relation to the nanostructured storage material. In some embodiments the cooling system includes a middle container within the container, separated by vacuum, an inner container with the middle container, and liquid nitrogen between the middle container and the inner container. The nanostructured storage material is within the inner container. Some embodiments contain a heater to control the temperature of the nanostructured storage material.
- FIG. 1 illustrates an element with sp2 bonds.
- FIG. 2A illustrates a plan view of a honeycomb nanostructured storage material.
- FIG. 2B illustrates a perspective view of a honeycomb nanostructured storage material, displaying the adsorbed hydrogen molecules.
- FIG. 3A illustrates a perspective view of a nanotube structure.
- FIG. 3B illustrates a perspective view of a nanotube structure, displaying the adsorbed hydrogen molecules.
- FIG. 4A illustrates a perspective view of a nanocage structure.
- FIG. 4B illustrates a perspective view of a nanocage structure, displaying the adsorbed hydrogen molecules.
- FIG. 5 illustrates the sorption and desorption curves of hydrogen in relation to a nanostructured storage material.
- FIG. 6 illustrates a cooled hydrogen storage system.
- FIG. 7 illustrates the temperature dependence of the hydrogen storage capacity in nanostructured storage materials.
- FIGS. 2A and 2B illustrate an embodiment for storing hydrogen in an sp2 bonded
nanostructured storage material 10 with a triangular lattice that has a flat planar network. - FIG. 2A shows the plan view of
nanostructured storage material 10 with a triangular lattice structure, without the hydrogen molecules. The chemical composition ofnanostructured storage material 10 is of the AB type, an example of which is boron nitride.Light elements 16 andlight elements 20 ofnanostructured storage material 10 are shown with bigger and smaller empty circles, respectively.Light elements - FIG. 2B shows a perspective view of the triangular lattice, wherein
hydrogen molecules 28 are shown in their bonding position. In someembodiments hydrogen molecules 28 are positioned over the center of the hexagons of the triangular lattice, in otherembodiments hydrogen molecules 28 are positioned over a bond or over an atom of the lattice. In some embodiments there is one energetically favored position forhydrogen molecules 28, in other embodiments there are several substantially equivalent positions. In some embodiments the orientation ofhydrogen molecules 28 can be parallel to the local plane of the triangular lattice, in other embodiments the orientation can be perpendicular, or it can make some other angle with the local plane of the triangular lattice. - The adsorption properties of hydrogen to
nanostructured storage material 10 depend on the nature of sp2 bonds 24. In some embodiments this property is used, when the adsorption properties of hydrogen tonanostructured storage material 10 are improved by modifying sp2 bonds 24. - Embodiments with modified sp2 bonds 24 are described, for example, in U.S. patent application entitled: “Increasing Hydrogen Adsorption For Hydrogen Storage In Nanostructured Materials By Modifying sp2 Covalent Bonds” by Young-Kyun Kwon, Seung-Hoon Jhi, Keith Bradley, Philip G. Collins, Jean-Christophe P. Gabriel, and George Grüner.
- In these embodiments sp2 bonds 24 are modified, for example, by forming non-planar structures, by introducing various defects, and by introducing different elements into
nanostructured storage material 10. In these embodiments the so far passive additional p electron may hybridize to a small degree with the elections, which formed the sp2 configuration. Therefore, in these embodiments sp2 bond 24 may acquire a small sp3 character. Thus, in these embodiments the covalent bonds ofnanostructured storage material 10 may be only substantially sp2 bonds. - FIGS. 3A and 32B illustrate some embodiment for storing hydrogen in an sp2 bonded
nanostructured storage material 10 with a planar triangular lattice that has been deformed into a tubular structure, or nanotube. - FIG. 3A shows a perspective view of the nanotube without the hydrogen molecules, where the chemical composition of
nanostructured storage material 10 is of the AB type, an example of which is boron nitride.Light elements 16 andlight elements 20 ofnanostructured storage material 10 are shown with bigger and smaller empty circles, respectively.Light elements - FIG. 3B shows a perspective view of the nanotube, wherein
hydrogen molecules 28 are shown in their bonding position. In someembodiments hydrogen molecules 28 are positioned over the center of the hexagons of the triangular lattice, in otherembodiments hydrogen molecules 28 are positioned over a bond or over an atom of the triangular lattice. In some embodiments there is one energetically favored position forhydrogen molecules 28, in other embodiments there are several substantially equivalent positions. In some embodiments the orientation ofhydrogen molecules 28 can be parallel to the local plane of the triangular lattice, in other embodiments the orientation can be perpendicular, or it can make some other angle with the local plane of the triangular lattice. - FIGS. 4A and 4B illustrate some embodiment for storing hydrogen in an sp2 bonded
nanostructured storage material 10 with a planar triangular lattice that has been deformed into a cage structure, or nanocage. - FIG. 4A shows a perspective view of the nanocage without the hydrogen, where the chemical composition of
nanostructured storage material 10 is of the AB type, an example of which is boron nitride.Light elements 16 andlight elements 20 ofnanostructured storage material 10 are shown with bigger and smaller empty circles, respectively.Light elements - FIG. 4B shows a perspective view of the nanocage, wherein
hydrogen molecules 28 are shown in their bonding position. In someembodiments hydrogen molecules 28 are positioned over the center of the hexagons of the triangular lattice, in otherembodiments hydrogen molecules 28 are positioned over a bond or over an atom of the triangular lattice. In some embodiments there is one energetically favored position forhydrogen molecules 28, in other embodiments there are several substantially equivalent positions. In some embodiments the orientation ofhydrogen molecules 28 can be parallel to the local plane of the triangular lattice, in other embodiments the orientation can be perpendicular, or it can make some other angle with the local plane of the triangular lattice. - In further embodiments hydrogen can be stored in other forms of
nanostructured storage material 10. A non-exhaustive list of possible forms ofnanostructured storage material 10 includes: - nanofibers of the following kinds: turbostatic, highly oriented, twisted, straight, curled and rigid;
- nanotubes of the following kinds: single walled, double walled, multi walled, with zig-zag chirality, or a mixture of chiralities, twisted, straight, bent, kinked, curled, flattened, and round;
- ropes of nanotubes, twisted nanotubes, braided nanotubes;
- small bundles of nanotubes (with a number of tubes less than ten), medium bundles of nanotubes (with a number of tubes in the hundreds), large bundles of nanotubes (with a number of tubes in the thousands);
- nanotorii, nanocoils, nanorods, nanowires, nanohorns;
- empty nanocages, filled nanocages, multifaceted nanocages, empty nanococoons, filled nanococoons, multifaceted nanococoons;
- thin nanoplatelets, thick nanoplatelets, intercalated nanoplatelets, with thickness of about 0.3 nm to about 100 nm, and lateral size of about 5 nm to about 500 nm.
- All these structures can assume heterogeneous forms. Heterogeneous forms include structures, where one part of the structure has a certain chemical composition, within another part of the structure has a different chemical composition. An example is a multi walled nanotube, where the chemical composition of the different walls can be different from each other.
- Heterogeneous forms also include different forms of
nanostructured storage material 10, where more than one of the above listed forms are joined into a larger irregular structure. Finally, all above d materials can have cracks, dislocations, branches or other imperfections. - It is understood that the scope of the invention extends to all the above listed and described forms of
nanostructured storage material 10. - Economic and practical considerations prefer hydrogen storage systems that are light. In particular, light storage systems have higher storage efficiency in the sense that the weight % of the stored hydrogen is higher in light storage systems. Therefore, embodiments of the present invention include
nanostructured storage material 10 composed of light elements. Suitable light elements include elements of the second and third rows of the periodic table: Be, B, C, N, O, F, Mg, P, S, and Cl. The storage efficiency ofnanostructured storage material 10 can be enhanced by combining the listed suitable light elements. While Al and Si containing nanostructures, such as zeolites, have been explored before for storage purposes, in some embodiments of the invention Al and Si can be combined with the above light elements. - Some embodiments can contain elements from other rows of the periodic table as well. Some of these elements can be introduced deliberately to enhance a desired property. Other elements may be a residue from the production process, for example, a catalyst. Therefore, it is understood that embodiments of the invention may contain heavier elements in some concentration.
- Some embodiments of the invention include BxCyNz, where x, y, and z are small integers. Making of this material is described, for example, in “Pyrolytically Grown Arrays of Highly Aligned BxCyNz Nantubes”, by W. -Q. Han, J. Cumings, and A. Zettl in Applied Physics Letters, vol. 78, p. 2769 (2001), and in U.S. Pat. No. 6,231,980 “BxCyNz nanotubes and nanoparticles,” by M. Cohen and A. Zettl, which publication and patent are hereby incorporated in their entirety by this reference.
- Some embodiments of the invention include BN. Making of this material is described, for example, in “Mass Production of Boron Nitride Double-wall Nanotubes and Nanococoons,” by J. Cumings and A. Zettl in Chemical Physics Letters, vol. 316, p. 211 (2000), hereby incorporated in its entirety by this reference.
- Some embodiments of the invention include BC2N. Making of this material is described, for example, in “Synthesis of BxCyNz Nanotubules,” by Z. Weng-Sieh, K. Cherrey, N. G. Chopra et al., in Physical Review B, vol. 51, p. 11229 (1995), hereby incorporated in its entirety by this reference.
- Some embodiments of the invention include MgB2. Making of this material is described, for example, in “Superconducing MgB2 Nanowires,” by Y. Wu, B. Messer, and P. Yang in Advanced Materials, vol. 13, p. 1487 (2001), hereby incorporated in its entirety by this reference.
- Some embodiments of the invention include Be3N2. Making of this material is described, for example, in “Die Struktur Einer Neuen Modifikation von Be3N2, ” by P. Eckerlin and A. Rabenau in Angewandte Chemie, vol. 304, p. 218 (1960), hereby incorporated in its entirety by this reference.
- Some embodiments of the invention include BeB2. Making of this material is described, for example, in “Absence of Superconductivity in BeB2, ” by I. Felner in Physica C, vol. 353, p. 11 (2001), hereby incorporated in its entirety by this reference.
- Some embodiments of the invention include B2O. Making of this material is described, for example, by H. Hall and L. Compton in Inorganic Chemistry, vol. 4, p. 1213 (1965), hereby incorporated in its entirety by this reference.
- Some embodiments of the invention include elemental boron. Making of this material is described, for example, by S. La Placa, P. Roland, and J. Wynne in Chemical Physics Letter vol. 190, p. 163 (1992), hereby incorporated in its entirety by this reference.
- Some embodiments of the invention include standard materials that are listed in the Chemical Abstract Service (CAS) at the web site: www.cas.org:
TABLE 1 Chemical composition CAS number BeO 1304-56-9 AlCl3 7784-13-6 Al4C3 1299-86-1 AlF3 7784-18-1 Al2O3 1344-28-1 Al2S3 1302-81-4 Mg2Si 22831-39-6 Mg3N2 12057-71-5 Li3N 26134-62-3 Li2S 12136-58-2 Na2S 1313-82-2 Na2S4 12034-39-8 - In the above embodiments of the invention the hydrogen atoms bonds to
nanostructured storage material 10 by physisorption. Therefore, the present invention differs from U.S. Pat. No. 5,653,951, which describes an invention, where “ . . . nanostructures of the present invention store hydrogen by chemisorbing molecular hydrogen in the interstices of the nanostructure” (col. 3, 11.40-42). - There are several crucial differences between physisorption and chemisorption. The following comparative table is assembled according to theKirk-Othmer Encyclopedia of Chemical Technology, John Wiley and Sons, (2001):
TABLE 2 Parameter Physisorption Chemisorption interaction no electron transfer; electron transfer, leading to of adsorption adsorption by physical the formation of a chemical interactions bond between adsorbate and surface acitivation small, often immeasurable considerable energy desorption rapid, non-activated slow, activated - As Table 2 states, chemisorption is a type of adsorption, where an adsorbate is bound to a surface by the transfer of electrons, forming a chemical bond between the adsorbate and atoms of the surface. In contrast, physisorption is a type of adsorption, where an adsorbate is bound to a surface by physical interactions without the transfer of electrons. Physical interactions, giving rise to physisorption, include, but are not restricted to, van der Waals interactions. Van der Waals interactions are operational when the neutral atoms or molecules of the adsorbate and the surface polarize each other, and the polarized atoms or molecules attract each other at some distance.
- Accordingly, chemisorptive bonds are strong and physisorptive bonds are weak. This difference manifests itself in the kinetics of the dissolution of the bonds, or desorption. Chemisorptive bonds are dissolved by an activated process, i.e., by thermal activation over an activation energy barrier, which is considerable. For this reason dissolution of chemisorbed bonds proceeds slowly and is not adiabatically reversible.
- In contrast, physisorptive bonds are dissolved by a non-activated process. The activation energy is small, in many cases immeasurably small. Hence physisorptive bonds dissolve rapidly and reversibly.
- U.S. Pat. No. 5,653,951 discusses in great detail the irreversible aspects of desorption of that invention. The irreversibility of desorption of that invention is illustrated in FIGS. 1A, 1B,2B, 3A, and 3B by the fact that the sorption and desorption curves do not coincide. Such irreversibility is strong evidence for the chemisorptive nature of hydrogen bonding in U.S. Pat. No. 5,653,951.
- FIG. 5 illustrates the coverage fraction, i.e., the fraction of the adsorbent surface, which is covered by hydrogen, as a function of pressure at a fixed temperature. The solid sorption curve indicates the results for starting at a low pressure value, for example, 10−3 atm, and measuring the coverage fraction while increasing the pressure. The dashed desorption curve indicates the results for starting at a high pressure value, for example, 1 atm, and measuring the coverage fraction while decreasing the pressure.
- In contrast to U.S. Pat. No. 5,653,951, as shown in FIG. 5, the sorption and desorption curves of the present invention substantially coincide, indicating that the adsorption occurs by physisorption.
- The above embodiments can be manufactured by different techniques. The two main acts of manufacturing are the making of
nanostructured storage material 10 and the subsequent purifying ofnanostructured storage material 10. - According to some methods of the invention, the making of
nanostructured storage material 10 starts by providing the bulk material with the desired chemical composition in polycrystalline or micrograined form. The bulk material is then loaded into a ball mill. The balls of the ball mill can be stainless steel balls or hard ceramic balls, with a diameter of, for example, about 3 mm. The material can be milled for an extended period, for example, 24 hours. The milling can take place in air, in vacuum, or in reactive gases. The resulting material will contain somenanostructured storage material 10, which can be separated by subsequent purifying. - According to some other methods of the invention, the making of
nanostructured storage material 10 starts with providing a bulk material in powder form. In some embodiments the bulk material has the desired chemical composition, in others the bulk material contains some of the desired ingredients. The powdered bulk material is pressed into a shape, suitable for functioning as an electrode, an example of such a shape being a rod. The rod is then used as an electrode to construct an arc chamber. The construction of such an arc chamber is described, for example, in “A Mass Production of Boron Nitride Double Wall Nanotubes and Nanocacoons,” by J. Cumings and A. Zettl in Chemical Physics Letters, vol. 316, p. 211 (2000). The arc chamber can be filled up with inert gases, for example, helium. In some embodiments the arc chamber can be filled up by one or more reactive gas. For example, beryllium nitride, Be3N2, could be made in an arc chamber whose electrode contains beryllium and where the chamber contains nitrogen gas. - Subsequent purifying of
nanostructured storage material 10 can be performed by many methods. Some purifying methods are described by A. Dillon et al. in Advanced Materials, vol. 11, p. 1354 (1999), G. Duesberg et al. in Applied Physics A, vol. 67, p. 117 (1998), K. Shelimov et al. in Chemical Physics Letters, vol. 282, p. 429 (1998), J. Tak et al. in Chemical Physics Letters, vol. 344, p. 18 (2001), P. Young et al. in Carbon, vol. 39, p. 655 (2001), which publications are hereby incorporated in their entirety by this reference. Purifying methods are capable of extractingnanostructured storage material 10 of a particular class and form, for example, corresponding to the above list ofnanostructured storage materials 10. - FIG. 6 illustrates an embodiment of a
hydrogen storage system 100 according to the invention. Anouter container 104 contains vacuum inouter region 108 to insulate the internal parts ofhydrogen storage system 100 from the heat of the environment. The vacuum inouter region 108 can be controlled through vacuum valve 110. A pump can be coupled to vacuum valve 110 to reduce the pressure inouter region 108. In some embodiments the pressure inouter region 108 is between about 109 atm and 10−1 atm, for example, 10−6 atm. -
Middle container 112 contains a coolingsubstance 116 to provide cooling ofhydrogen storage system 100. Coolingsubstance 116 can be, for example, liquid nitrogen. - Cooling systems utilizing liquid nitrogen have multiple advantages over systems utilizing liquid helium. Liquid nitrogen is much cheaper per liter than liquid helium. Nitrogen becomes a liquid at 77 K, whereas helium becomes a liquid at 4.2 K. It requires much less energy to cool a system to a temperature of 77 K, than to a temperature of 4.2 K. It also requires a much simpler, and therefore lighter cooling apparatus to maintain a temperature of 77 K, than to maintain a temperature of 4.2 K.
- Cooling
valve 114 is used to control the cooling substance. For example, coolingsubstance 116 can be supplied throughcooling valve 114, and the evaporatedexcess cooling substance 116 can be released throughcooling valve 114. In embodiments that use different hydrogen storage materials other coolingsubstances 116 may be utilized. - Inner container120 contains
nanostructured storage material 10.Nanostructured storage material 10 can be any embodiment described above or a combination thereof. In some embodimentsnanostructured storage material 10 substantially fills up inner container 120. In other embodimentsnanostructured storage material 10 is combined with a hydrogen distribution system, which provides paths for the hydrogen to flow efficiently across the volume ofnanostructured storage material 10. The hydrogen distribution system can be, for example, a hierarchical network of tubes of varying diameters to facilitate the efficient flow of hydrogen. - A
hydrogen valve 126 is used to control the hydrogen gas.Hydrogen storage system 100 can be filled by couplinghydrogen valve 126 to a hydrogen container through a pump. - FIG. 7 illustrates the hydrogen storage capacity in percents in
nanostructured storage material 10 as a function of the temperature. The amount of stored hydrogen is normalized with the amount stored at zero temperature. The curves refer to pressures of 1 atm, 10 atm, and 100 atm. FIG. 7 illustrates that as the temperature is increased from a low value, hydrogen starts the desorption at a relatively well defined desorption temperature TD. The value of TD depends on the pressure, as shown. When the temperature is raised to about 120% of TD at 1 atm, and to about 150% of TD at 100 atm, substantially all hydrogen is released. The value of TD is about 60 K for carbon nanostructures and higher for boron nitride nanostructures. In FIG. 7 the temperature is given relative to the desorption temperature TD at 1 atm, TD(1 atm). - The amount of hydrogen adsorbed in a storage material can be characterized by the percentage wise weight increase of the storage system caused by the adsorption of hydrogen, in units of weight %.
- Several papers addressed the storage of hydrogen in nanostructures at ambient temperatures. For most nanostructured materials the desorption temperature is well below ambient temperature, in accordance with the fact that physisorptive bonds are weak. Therefore, the amount of hydrogen stored in these nanostructures at ambient temperature is rather small. For example, M. Ashraf Imam and R. Loufty report in “Hydrogen Adsorption of Different Types of Nanotubes,” on p. 40 of the Procedings of NT'01, the International Workshop of on the Science and Applications of Nanotubes, hereby incorporated in its entirety by this reference, that single walled nanotubes adsorb hydrogen in an amount between about 0.30 weight % and about 0.50 weight %.
- In contrast, embodiments of the invention store hydrogen in cooled storage systems at temperatures below the desorption temperature, enabling the storage of much larger quantities. In the above units hydrogen adsorption below the desorption temperature in some embodiments is between about 3 weight % and about 27 weight %, for example, 7.5 weight %. Operating
hydrogen storage system 100 below the desorption temperature enhances the storage capacity by a factor of 30 or more in comparison to operating thehydrogen storage system 100 at ambient temperatures. - At the same time embodiments of the invention are operated at or above liquid nitrogen temperatures, and thus do not require the use of liquid helium for cooling purposes. As discussed above, cooling systems using liquid nitrogen have many advantages over cooling systems using liquid helium.
- Storage systems that advantageously use liquid nitrogen as cooling
substance 116 require nanostructured storage materials 124 that have a desorption temperature above 77 K. The desorption temperature ofnanostructured storage material 10 depends on its chemical composition. In particular, while pure carbon nanostructures typically have desorption temperatures below 77 K, embodiments that use nanostructured storage materials 124 formed from a combination of light elements have desorption temperatures well above 77 K. For example, boron nitride has a desorption temperature which is about 30% higher than that of carbon. - Storage systems with higher desorption temperatures require less energy for their operation. In particular, storage systems with desorption temperatures at or above the ambient temperature do not require a cooling system, making the storage system much lighter. Suitable selection of the chemical composition of
nanostructured storage material 10 may increase the desorption temperature to ambient temperature. - The operation of
hydrogen storage system 100 includes filling up the system with hydrogen and recovering stored hydrogen from the system. -
Hydrogen storage system 100 can be filled up by couplinghydrogen valve 126 to a hydrogen container through a pump.Nanostructured storage material 10 is cooled by coolingsubstance 116 to temperatures below the desorption temperature. When the pressure of the pump is raised to a suitable value, hydrogen from the hydrogen container will be pumped into inner container 120, where it will adsorb tonanostructured storage material 10. Suitable pressure values can lie in the range of, for example, about 1 atm to about 20 atm. - Hydrogen can be recovered from
hydrogen storage system 100 by various methods. Some embodiments recover the hydrogen by heatingnanostructured storage material 10 withheater 130.Heater 130 can be, for example, a resistor, driven by a current. The longer the current is applied toheater 130, or the more current is applied toheater 130, the higher the temperature ofnanostructured storage material 10 will rise. As the temperature rises above the desorption temperature, hydrogen will desorb fromnanostructured storage material 10, and can be recovered throughhydrogen valve 126. In some other embodiments simply the leakage heat, leaking into inner container 120 from the outside, can be used to drive the desorption of hydrogen. - Although the various aspects of the present invention have been described with respect to certain embodiments, it is understood that the invention is entitled to protection within the full scope of the appended claims.
Claims (40)
1. A hydrogen storage nanostructure, comprising:
a nanostructured storage material, comprising
a plurality of light elements, wherein the light elements are selected from the group consisting of Be, B, C, N, O, F, Mg, P, S, and Cl, wherein
the nanostructured storage material is adapted to adsorb hydrogen by physisorption.
2. The hydrogen storage nanostructure of claim 1 , wherein
the nanostructured storage material is adapted to adsorb hydrogen without the formation of a chemical bond.
3. The hydrogen storage nanostructure of claim 1 , wherein
the nanostructured storage material is adapted to adsorb hydrogen with van der Waals interactions.
4. The hydrogen storage nanostructure of claim 1 , wherein
the chemical composition of the nanostructured storage material is selected from the group consisting of BxCyNz, BN, BC2N, MgB2, Be3N2, BeB2, B2O, B, BeO, AlCl3, Al4C3, AlF3, Al2O3, Al2S3, Mg2Si, Mg3N2, Li3N, Li2S, Na2S, and Na2S4, wherein
the nanostructured storage material has a chemical composition; and
x, y, and z are integers.
5. The hydrogen storage nanostructure of claim 4 , wherein
the chemical composition of the nanostructured storage material is such that the desorption temperature of hydrogen in relation to the nanostructured storage material is greater than the liquefaction temperature of nitrogen, wherein the hydrogen has a desorption temperature in relation to the nanostructured storage material.
6. The hydrogen storage nanostructure of claim 1 , wherein the nanostructured storage material comprises:
a network of the plurality of light elements coupled with covalent bonds.
7. The hydrogen storage nanostructure of claim 6 , wherein the covalent bonds comprise:
substantially sp2 bonds.
8. The hydrogen storage nanostructure of claim 1 , wherein the nanostructured storage material comprises:
a layered network of the plurality of light elements.
9. The hydrogen storage nanostructure of claim 1 , wherein the nanostructured storage material comprises:
at least one of a triangular lattice, a nanofiber, a nanoplatelet, a single walled nanotube, a multi walled nanotube, a nanorod, a nanowire, and a fullerene.
10. The hydrogen storage nanostructure of claim 9 , wherein
the at least one of a triangular lattice, a nanofiber, a nanoplatelet, a single walled nanotube, a multi walled nanotube, a nanocage, a nanococoon, a nanohorn, a nanorope, a nanotorus, a nanocoil, a nanorod, a nanowire, and a fullerene-like molecule is in a heterogeneous form.
11. A hydrogen storage nanostructure, comprising:
a nanostructured storage material, comprising
at least one light element, wherein the at least one light element is selected from the group consisting of Be, B, N, P, and S, wherein
the nanostructured storage material is adapted to adsorb hydrogen by physisorption.
12. A hydrogen storage system, comprising:
a container; and
a nanostructured storage material, disposed within the container, wherein
the nanostructured storage material comprises a plurality of light elements, wherein the light elements are selected from the group consisting of Be, B, C, N, O, F, Mg, P, S, and Cl; and
the nanostructured storage material is adapted to adsorb hydrogen by physisorption.
13. The hydrogen storage system of claim 12 , wherein
the nanostructured storage material is adapted to adsorb hydrogen without the formation of a chemical bond.
14. The hydrogen storage system of claim 12 , wherein
nanostructured storage material is adapted to adsorb hydrogen by van der Waals interactions.
15. The hydrogen storage system of claim 12 , wherein
the chemical composition of the nanostructured storage material is selected from the group consisting of BxCyNz, BN, BC2N, MgB2, Be3N2, BeB2, B2O, B, BeO, AlCl3, Al4C3, Alf3, Al2O3, Al2S3, Mg2Si, Mg3N2, Li3N, Li2S, Na2S, and Na2S4, wherein
the nanostructured storage material has a chemical composition; and
x, y, and z are integers.
16. The hydrogen storage system of claim 15 , wherein
the chemical composition of the nanostructured storage material is such that the desorption temperature of hydrogen in relation to the nanostructured storage material is greater than the liquefaction temperature of nitrogen, wherein hydrogen has a desorption temperature in relation to the nanostructured storage material.
17. The hydrogen storage system of claim 12 , wherein the nanostructured storage material comprises:
a network of the plurality of light elements coupled with covalent bonds.
18. The hydrogen storage system of claim 17 , wherein the covalent bonds comprise:
substantially sp2 bonds.
19. The hydrogen storage system of claim 12 , wherein the nanostructured storage material comprises:
a layered network of the plurality of light elements.
20. The hydrogen storage system of claim 19 , wherein the layered network comprises:
at least one of a triangular lattice, a nanofiber, a nanoplatelet, a single walled nanotube, a multi walled nanotube, a nanocage, a nanococoon, a nanohorn, a nanorope, a nanotorus, a nanocoil, nanorod, a nanowire, and a fullerene.
21. The hydrogen storage system of claim 20 , wherein
the at least one of a triangular lattice, a nanofiber, a nanoplatelet, a single walled nanotube, a multi walled nanotube, a nanocage, a nanococoon, a nanohorn, a nanorope, a nanotorus, a nanocoil, a nanorod, a nanowire, and a fullerene-like molecule is in heterogeneous form.
22. The hydrogen storage system of claim 12 , wherein the nanostructured storage material is combined with a hydrogen distribution system within the container.
23. The hydrogen storage system of claim 12 , further comprising:
a cooling system, capable of cooling the nanostructured storage material below the desorption temperature of hydrogen in relation to the nanostructured storage material.
24. The hydrogen storage system of claim 23 , wherein the cooling system comprises:
a middle container, disposed within the container;
a heat insulator, disposed between the container and the middle container, capable of reducing the exchange of heat between the container and the middle container;
an inner container, disposed within the middle container; and
a cooling substance, disposed between the middle container and the inner container, capable of reducing the temperature of the inner container.
25. The hydrogen storage system of claim 24 , wherein
the heat insulator is a gaseous substance, having a pressure less than 10−1 atm.
26. The hydrogen storage system of claim 24 , wherein
the cooling substance is liquid nitrogen.
27. The hydrogen storage system of claim 24 , further comprising:
a heat insulating valve, coupled to the container, capable of controlling the heat insulator;
a cooling valve, coupled to the middle container, capable of controlling the cooling substance; and
a hydrogen valve, coupled to the inner container, capable of controlling the hydrogen.
28. The hydrogen storage system of 24, further comprising:
a heater, disposed within the inner container, capable of controlling the temperature of the nanostructured storage material.
29. The hydrogen storage system of claim 24 , further comprising:
a fuel cell, wherein the hydrogen recovered from the hydrogen storage system is used in the fuel cell to generate energy.
30. A hydrogen storage system, comprising:
container means; and
nanostructured storage means, disposed within the container means, wherein
the nanostructured storage means comprises a plurality of light elements, wherein the light elements are selected from the group consisting of Be, B, C, N, O, F, Mg, P, S, and Cl; and
the nanostructured storage means is adapted to adsorb hydrogen by physisorption.
31. A hydrogen storage system, comprising:
a container; and
a nanostructured storage material, disposed in the container, wherein
the nanostructured storage material comprises at least one light element, wherein
the at least one light element is selected from the group consisting of Be, B, N, P, and S; and
the nanostructured storage material is adapted to adsorb hydrogen by physisorption.
32. A hydrogen storage nanostructure, comprising:
a nanostructured storage material, comprising a plurality of light elements, wherein the light elements are selected from the group consisting of Be, B, C, N, O, F, Mg, Al, Si, P, S, and Cl, wherein
the nanostructured storage material is not a microporous material or zeolite, wherein
the nanostructured storage material is adapted to adsorb hydrogen by physisorption.
33. A method of storing hydrogen, the method comprising:
providing a nanostructured storage material in a container, the nanostructured storage material comprising:
a plurality of light elements, wherein the light elements are selected from the group consisting of Be, B, C, N, O, F, Mg, P, S, and Cl; and
introducing hydrogen into the nanostructured storage material,
wherein the hydrogen adsorbs to the nanostructured storage material by physisorption.
34. The method of claim 33 , wherein providing the nanostructured storage material comprises:
selecting the chemical composition of the nanostructured storage material so that the desorption temperature of hydrogen in relation to the nanostructured storage material is greater than the liquefaction temperature of nitrogen, wherein hydrogen has a desorption temperature in relation to the nanostructured storage material, and wherein the nanostructured storage material has a chemical composition.
35. The method of claim 33 , wherein providing the nanostructured storage material comprises:
providing the nanostructured storage material in combination with a hydrogen distribution system within an inner container.
36. The method of claim 33 , further comprising:
cooling the nanostructured storage material below the desorption temperature of the hydrogen in relation to the nanostructured storage material.
37. The method of claim 36 , wherein cooling the nanostructured storage material comprises:
providing a middle container, disposed within the container;
providing a heat insulator, disposed between the container and the middle container, capable of reducing the exchange of heat between the container and the middle container;
providing an inner container, disposed within the middle container; and
providing a cooling substance, disposed between the middle container and the inner container, capable of reducing the temperature of the inner container.
38. The method of claim 37 , wherein providing the cooling substance comprises:
providing liquid nitrogen, as a cooling substance.
39. The method of claim 37 , further comprising:
controlling the heat insulator with a heat insulating valve, coupled to the container;
controlling the cooling substance with a cooling valve, coupled to the middle container; and
controlling the hydrogen with a hydrogen valve, coupled to the inner container.
40. The method of claim 37 , further comprising:
controlling the temperature of the nanostructured material with a heater, disposed within the inner container.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/404,303 US20030167778A1 (en) | 2001-12-11 | 2003-03-31 | Hydrogen storage in nanostructures with physisorption |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/020,392 US6672077B1 (en) | 2001-12-11 | 2001-12-11 | Hydrogen storage in nanostructure with physisorption |
US10/404,303 US20030167778A1 (en) | 2001-12-11 | 2003-03-31 | Hydrogen storage in nanostructures with physisorption |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/020,392 Continuation US6672077B1 (en) | 2001-12-11 | 2001-12-11 | Hydrogen storage in nanostructure with physisorption |
Publications (1)
Publication Number | Publication Date |
---|---|
US20030167778A1 true US20030167778A1 (en) | 2003-09-11 |
Family
ID=21798383
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/020,392 Expired - Lifetime US6672077B1 (en) | 2001-12-11 | 2001-12-11 | Hydrogen storage in nanostructure with physisorption |
US10/404,303 Abandoned US20030167778A1 (en) | 2001-12-11 | 2003-03-31 | Hydrogen storage in nanostructures with physisorption |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/020,392 Expired - Lifetime US6672077B1 (en) | 2001-12-11 | 2001-12-11 | Hydrogen storage in nanostructure with physisorption |
Country Status (3)
Country | Link |
---|---|
US (2) | US6672077B1 (en) |
AU (1) | AU2002359677A1 (en) |
WO (1) | WO2003050447A1 (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040067530A1 (en) * | 2002-05-08 | 2004-04-08 | The Regents Of The University Of California | Electronic sensing of biomolecular processes |
US20040209144A1 (en) * | 2003-04-16 | 2004-10-21 | Pavel Kornilovich | Gas storage medium and methods |
US20050208376A1 (en) * | 2004-03-16 | 2005-09-22 | The Regents Of The University Of California | Nanostructured materials for hydrogen storage |
FR2871478A1 (en) * | 2004-06-15 | 2005-12-16 | Arash Mofakhami | CATION-ELECTRON INTRUSION AND COLLISION SYSTEM IN NON-CONDUCTIVE MATERIAL |
US20060062712A1 (en) * | 2004-09-20 | 2006-03-23 | Pak Chan-Ho | Method of preparing carbon nanocages |
EP1707867A1 (en) * | 2005-03-30 | 2006-10-04 | Northrop Grumman Corporation | Reduced boiloff cryogen storage |
US20060218940A1 (en) * | 2005-03-30 | 2006-10-05 | Starkovich John A | Reduced boiloff cryogen storage |
US20080009002A1 (en) * | 2004-11-09 | 2008-01-10 | The Regents Of The University Of California | Analyte Identification Using Electronic Devices |
US20090000192A1 (en) * | 2005-06-24 | 2009-01-01 | Washington State University Research Foundation | Apparatus with high surface area nanostructures for hydrogen storage, and methods of storing hydrogen |
JP2009501068A (en) * | 2005-06-24 | 2009-01-15 | ワシントン ステイト ユニヴァーシティー リサーチ ファウンデーション | Method for manufacturing and coating nanostructured components |
US20090278556A1 (en) * | 2006-01-26 | 2009-11-12 | Nanoselect, Inc. | Carbon Nanostructure Electrode Based Sensors: Devices, Processes and Uses Thereof |
US20090282839A1 (en) * | 2008-05-15 | 2009-11-19 | Sigal Richard F | Apparatus and method of storing and transporting a gas |
US20110053020A1 (en) * | 2007-11-09 | 2011-03-03 | Washington State University Research Foundation | Catalysts and related methods |
GB2482311A (en) * | 2010-07-28 | 2012-02-01 | Sharp Kk | II-III-N and II-N semiconductor nanoparticles, comprising the Group II elements Zinc (Zn) or Magensium (Mg) |
US8907384B2 (en) | 2006-01-26 | 2014-12-09 | Nanoselect, Inc. | CNT-based sensors: devices, processes and uses thereof |
Families Citing this family (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8958917B2 (en) * | 1998-12-17 | 2015-02-17 | Hach Company | Method and system for remote monitoring of fluid quality and treatment |
US9056783B2 (en) * | 1998-12-17 | 2015-06-16 | Hach Company | System for monitoring discharges into a waste water collection system |
US20110125412A1 (en) * | 1998-12-17 | 2011-05-26 | Hach Company | Remote monitoring of carbon nanotube sensor |
US7454295B2 (en) | 1998-12-17 | 2008-11-18 | The Watereye Corporation | Anti-terrorism water quality monitoring system |
DE10052856A1 (en) * | 2000-10-24 | 2002-04-25 | Linde Ag | Storage container for cryogenic media has inner and outer containers and a further storage space connected to emptying pipe of storage container through active connection e.g. heat exchanger |
US7024869B2 (en) * | 2002-12-16 | 2006-04-11 | Air Products And Chemicals, Inc. | Addition of odorants to hydrogen by incorporating odorants with hydrogen storage materials |
US8920619B2 (en) | 2003-03-19 | 2014-12-30 | Hach Company | Carbon nanotube sensor |
US6988370B2 (en) * | 2003-06-12 | 2006-01-24 | Michael Iarocci | Cryogenic storage system with improved temperature control |
US8211593B2 (en) * | 2003-09-08 | 2012-07-03 | Intematix Corporation | Low platinum fuel cells, catalysts, and method for preparing the same |
US7351444B2 (en) * | 2003-09-08 | 2008-04-01 | Intematix Corporation | Low platinum fuel cell catalysts and method for preparing the same |
US20050112450A1 (en) * | 2003-09-08 | 2005-05-26 | Intematix Corporation | Low platinum fuel cell catalysts and method for preparing the same |
KR20060120033A (en) * | 2003-09-30 | 2006-11-24 | 제너럴 일렉트릭 캄파니 | Hydrogen storage compositions and methods of manufacture thereof |
US7175826B2 (en) | 2003-12-29 | 2007-02-13 | General Electric Company | Compositions and methods for hydrogen storage and recovery |
US7115247B2 (en) * | 2003-09-30 | 2006-10-03 | General Electric Company | Hydrogen storage compositions and methods of manufacture thereof |
US7029517B2 (en) | 2003-11-06 | 2006-04-18 | General Electric Company | Devices and methods for hydrogen storage and generation |
US20060163160A1 (en) * | 2005-01-25 | 2006-07-27 | Weiner Michael L | Halloysite microtubule processes, structures, and compositions |
US7491263B2 (en) * | 2004-04-05 | 2009-02-17 | Technology Innovation, Llc | Storage assembly |
US7425232B2 (en) * | 2004-04-05 | 2008-09-16 | Naturalnano Research, Inc. | Hydrogen storage apparatus comprised of halloysite |
WO2005107645A2 (en) * | 2004-04-05 | 2005-11-17 | Technology Innovations, Llc | Hydrogen storage apparatus comprised of halloysite |
US20050229488A1 (en) * | 2004-04-19 | 2005-10-20 | Texaco Inc. | Method and apparatus for providing a continuous stream of reformate |
US20060076354A1 (en) * | 2004-10-07 | 2006-04-13 | Lanzafame John F | Hydrogen storage apparatus |
US7400490B2 (en) | 2005-01-25 | 2008-07-15 | Naturalnano Research, Inc. | Ultracapacitors comprised of mineral microtubules |
FR2881733B1 (en) * | 2005-02-07 | 2008-02-08 | Inst Francais Du Petrole | NEW HYDROGEN STORAGE MATERIAL COMPRISING A BALANCED SYSTEM BETWEEN AN ALLOY OF MAGNESIUM AND NITROGEN AND THE CORRESPONDING HYDRIDE |
DE102005023036B4 (en) * | 2005-05-13 | 2007-05-31 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Hydrogen storage and hydrogen storage method |
KR100979470B1 (en) * | 2005-08-08 | 2010-09-02 | 도요타 지도샤(주) | Hydrogen storage device |
JP4929654B2 (en) * | 2005-09-02 | 2012-05-09 | トヨタ自動車株式会社 | Hydrogen storage device |
DE102006019993B3 (en) * | 2006-04-26 | 2007-12-27 | Daimlerchrysler Ag | Compressed gas e.g. hydrogen, storage for e.g. fuel cell vehicle, has cooling device provided for heat transfer medium, where part of gas is supplied as heat transfer medium to cooling device through branching of filling device |
DE102006027179A1 (en) * | 2006-06-12 | 2007-12-13 | Bayerische Motoren Werke Ag | Fuel storage device for a motor vehicle operated with hydrogen |
KR100910059B1 (en) | 2006-12-06 | 2009-07-30 | 한국전자통신연구원 | Gas storage medium, gas storage apparatus and method |
US8673436B2 (en) * | 2006-12-22 | 2014-03-18 | Southwest Research Institute | Nanoengineered material for hydrogen storage |
US7648568B2 (en) * | 2007-01-11 | 2010-01-19 | Gm Global Technology Operations, Inc. | Hydrogen storage tank system based on gas adsorption on high-surface materials comprising an integrated heat exchanger |
WO2008124167A1 (en) * | 2007-04-10 | 2008-10-16 | The Regents Of The University Of California | Charge storage devices containing carbon nanotube films as electrodes and charge collectors |
DE102007025217B9 (en) * | 2007-05-31 | 2010-04-29 | Airbus Deutschland Gmbh | Apparatus and method for storing hydrogen for an aircraft |
DE102007058671B4 (en) | 2007-12-06 | 2016-04-28 | Basf Se | Method for controlling the gas extraction and device for storing at least one gas |
DE102007058673B4 (en) * | 2007-12-06 | 2016-04-14 | Basf Se | Method for storing gaseous hydrocarbons and apparatus therefor |
DE102009000508A1 (en) * | 2008-07-29 | 2010-02-04 | Robert Bosch Gmbh | Storage container for storage of fuel in fuel cell system of motor vehicle, has cooling jacket peripherally surrounding reservoir and serving for cooling of fuel, where fuel is reversibly adsorbed into adsorption element of reservoir |
US20100059528A1 (en) * | 2008-09-11 | 2010-03-11 | C. En. Limited | Apparatus for gas storage |
DE102008043927A1 (en) | 2008-11-20 | 2010-05-27 | Robert Bosch Gmbh | Removing gases from a sorption accumulator, comprises removing gas from accumulator up to reaching predetermined working pressure at constant removal temperature, and removing gas from accumulator up to reaching minimum removal pressure |
DE102010010108B4 (en) * | 2010-02-23 | 2012-01-26 | Institut für Luft- und Kältetechnik gGmbH | Method of storing and storing natural gas |
DE102009020138B3 (en) * | 2009-05-06 | 2010-12-02 | Institut für Luft- und Kältetechnik gGmbH | Method for storing industrial gas in thermally insulated, pressure-tight storage tank of motor vehicle, involves using accumulator to store gas at temperature close to critical point and at pressure higher than given critical pressure |
WO2012049622A1 (en) | 2010-10-15 | 2012-04-19 | Phiroze H Patel | An adsorbent system and an apparatus for effective storing and fuelling of hydrogen |
EP3630677A4 (en) | 2017-05-31 | 2021-03-03 | Hydrogen in Motion Inc. (H2M) | Hydrogen storage product and method for manufacturing same |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4960450A (en) | 1989-09-19 | 1990-10-02 | Syracuse University | Selection and preparation of activated carbon for fuel gas storage |
US5458784A (en) | 1990-10-23 | 1995-10-17 | Catalytic Materials Limited | Removal of contaminants from aqueous and gaseous streams using graphic filaments |
US6231980B1 (en) | 1995-02-14 | 2001-05-15 | The Regents Of The University Of California | BX CY NZ nanotubes and nanoparticles |
NO307986B1 (en) | 1998-02-06 | 2000-07-03 | Inst Energiteknik | Method of storing hydrogen in a carbon material |
US6159538A (en) | 1999-06-15 | 2000-12-12 | Rodriguez; Nelly M. | Method for introducing hydrogen into layered nanostructures |
-
2001
- 2001-12-11 US US10/020,392 patent/US6672077B1/en not_active Expired - Lifetime
-
2002
- 2002-12-10 WO PCT/US2002/039695 patent/WO2003050447A1/en not_active Application Discontinuation
- 2002-12-10 AU AU2002359677A patent/AU2002359677A1/en not_active Abandoned
-
2003
- 2003-03-31 US US10/404,303 patent/US20030167778A1/en not_active Abandoned
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040067530A1 (en) * | 2002-05-08 | 2004-04-08 | The Regents Of The University Of California | Electronic sensing of biomolecular processes |
US7135057B2 (en) * | 2003-04-16 | 2006-11-14 | Hewlett-Packard Development Company, L.P. | Gas storage medium and methods |
US20040209144A1 (en) * | 2003-04-16 | 2004-10-21 | Pavel Kornilovich | Gas storage medium and methods |
US20050208376A1 (en) * | 2004-03-16 | 2005-09-22 | The Regents Of The University Of California | Nanostructured materials for hydrogen storage |
US7303736B2 (en) | 2004-03-16 | 2007-12-04 | The Regents Of The University Of California | Nanostructured materials for hydrogen storage |
WO2006003328A1 (en) * | 2004-06-15 | 2006-01-12 | Nassar, Tarek | System for cation-electron intrusion and collision in a non-conductive material |
AU2005259043B2 (en) * | 2004-06-15 | 2011-03-10 | Ceram Hyd | System for cation-electron intrusion and collision in a non-conductive material |
JP2008502568A (en) * | 2004-06-15 | 2008-01-31 | ナッサール,タレク | A system for cation-electron intrusion and collisions in non-conductive materials. |
US20080160359A1 (en) * | 2004-06-15 | 2008-07-03 | Arash Mofakhami | System For Cation-Electron Intrusion and Collision in a Non-Conductive Material |
FR2871478A1 (en) * | 2004-06-15 | 2005-12-16 | Arash Mofakhami | CATION-ELECTRON INTRUSION AND COLLISION SYSTEM IN NON-CONDUCTIVE MATERIAL |
US8083904B2 (en) | 2004-06-15 | 2011-12-27 | Ceram Hyd | System for cation-electron intrusion and collision in a non-conductive material |
US20060062712A1 (en) * | 2004-09-20 | 2006-03-23 | Pak Chan-Ho | Method of preparing carbon nanocages |
CN100391831C (en) * | 2004-09-20 | 2008-06-04 | 三星Sdi株式会社 | Method of preparing carbon nanocages |
US7518045B2 (en) | 2004-09-20 | 2009-04-14 | Samsung Sdi Co., Ltd. | Method of preparing carbon nanocages |
US20080009002A1 (en) * | 2004-11-09 | 2008-01-10 | The Regents Of The University Of California | Analyte Identification Using Electronic Devices |
EP1707867A1 (en) * | 2005-03-30 | 2006-10-04 | Northrop Grumman Corporation | Reduced boiloff cryogen storage |
US20060218940A1 (en) * | 2005-03-30 | 2006-10-05 | Starkovich John A | Reduced boiloff cryogen storage |
US20090000192A1 (en) * | 2005-06-24 | 2009-01-01 | Washington State University Research Foundation | Apparatus with high surface area nanostructures for hydrogen storage, and methods of storing hydrogen |
JP2009501068A (en) * | 2005-06-24 | 2009-01-15 | ワシントン ステイト ユニヴァーシティー リサーチ ファウンデーション | Method for manufacturing and coating nanostructured components |
US7771512B2 (en) * | 2005-06-24 | 2010-08-10 | Washington State University Research Foundation | Apparatus with high surface area nanostructures for hydrogen storage, and methods of storing hydrogen |
US20100215915A1 (en) * | 2005-06-24 | 2010-08-26 | Washington State University | Method for manufacture and coating of nanostructured components |
US20100276304A1 (en) * | 2005-06-24 | 2010-11-04 | Washington State University Research Foundation | Apparatus with high surface area nanostructures for hydrogen storage, and methods of storing hydrogen |
US8404212B2 (en) | 2005-06-24 | 2013-03-26 | Washington State University Research Foundation | Apparatus with high surface area nanostructures for hydrogen storage, and methods of storing hydrogen |
US20090278556A1 (en) * | 2006-01-26 | 2009-11-12 | Nanoselect, Inc. | Carbon Nanostructure Electrode Based Sensors: Devices, Processes and Uses Thereof |
US8907384B2 (en) | 2006-01-26 | 2014-12-09 | Nanoselect, Inc. | CNT-based sensors: devices, processes and uses thereof |
US20110053020A1 (en) * | 2007-11-09 | 2011-03-03 | Washington State University Research Foundation | Catalysts and related methods |
US20090282839A1 (en) * | 2008-05-15 | 2009-11-19 | Sigal Richard F | Apparatus and method of storing and transporting a gas |
GB2482311A (en) * | 2010-07-28 | 2012-02-01 | Sharp Kk | II-III-N and II-N semiconductor nanoparticles, comprising the Group II elements Zinc (Zn) or Magensium (Mg) |
JP2012031057A (en) * | 2010-07-28 | 2012-02-16 | Sharp Corp | Ii-iii-n semiconductor nanoparticle, and method of manufacturing the same |
US8900489B2 (en) | 2010-07-28 | 2014-12-02 | Sharp Kabushiki Kaisha | II-III-N semiconductor nanoparticles and method of making same |
US9985173B2 (en) | 2010-07-28 | 2018-05-29 | Sharp Kabushiki Kaisha | II-III-N semiconductor nanoparticles and method of making same |
Also Published As
Publication number | Publication date |
---|---|
WO2003050447A1 (en) | 2003-06-19 |
AU2002359677A1 (en) | 2003-06-23 |
US6672077B1 (en) | 2004-01-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6672077B1 (en) | Hydrogen storage in nanostructure with physisorption | |
US6872330B2 (en) | Chemical manufacture of nanostructured materials | |
Bai et al. | Storage of mechanical energy based on carbon nanotubes with high energy density and power density | |
EP1209119B1 (en) | Hydrogen storage using carbon-metal hybrid compositions | |
Rao et al. | Nanotubes | |
Ströbel et al. | Hydrogen storage by carbon materials | |
US6471936B1 (en) | Method of reversibly storing H2 and H2 storage system based on metal-doper carbon-based materials | |
Terrones | Carbon nanotubes: synthesis and properties, electronic devices and other emerging applications | |
US7771512B2 (en) | Apparatus with high surface area nanostructures for hydrogen storage, and methods of storing hydrogen | |
Zhu et al. | Hydrogen adsorption in bundles of well-aligned carbon nanotubes at room temperature | |
US20050075245A1 (en) | Carbon-based compositions for reversible hydrogen storage | |
US20070092437A1 (en) | Increasing hydrogen adsorption of nanostructured storage materials by modifying sp2 covalent bonds | |
JPH1072201A (en) | Hydrogen storage method | |
Bünger et al. | Hydrogen storage in carbon nanostructures–still a long road from science to commerce? | |
Rakhi | Preparation and properties of manipulated carbon nanotube composites and applications | |
WO2006095800A1 (en) | Hydrogen storage material, hydrogen storage structure, hydrogen storer, hydrogen storage apparatus, fuel cell vehicle, and process for producing hydrogen storage material | |
WO2005120715A2 (en) | Electrostatic switch for hydrogen storage and release from hydrogen storage media | |
JP5089080B2 (en) | Hydrogen storage material and method for producing the same | |
Jiang | CVD growth of carbon nanofibers | |
Collins | a) United States Patent | |
US20060191409A1 (en) | Electrostatic switch for hydrogen storage and release from hydrogen storage media | |
JP4456712B2 (en) | Hydrogen gas storage material and storage method | |
KR101400228B1 (en) | Nano porous material, method for preparing the nano porous material and hydrogen strorage device employing the same | |
Rao et al. | Nanostructured forms of carbon: an overview | |
KR20100004023A (en) | Hydrogen storage material and hydrogen strorage device employing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: NANOMIX, INC., CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BRADLEY, KEITH;COLLINS, PHILIP G.;GABRIEL, JEAN-CHRISTOPHE;AND OTHERS;REEL/FRAME:013939/0401 Effective date: 20030331 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |