WO2005107645A2 - Appareil de stockage d'hydrogene constitue d'halloysite - Google Patents

Appareil de stockage d'hydrogene constitue d'halloysite Download PDF

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Publication number
WO2005107645A2
WO2005107645A2 PCT/US2005/011473 US2005011473W WO2005107645A2 WO 2005107645 A2 WO2005107645 A2 WO 2005107645A2 US 2005011473 W US2005011473 W US 2005011473W WO 2005107645 A2 WO2005107645 A2 WO 2005107645A2
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WO
WIPO (PCT)
Prior art keywords
halloysite
rods
hydrogen
recited
substrate
Prior art date
Application number
PCT/US2005/011473
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English (en)
Other versions
WO2005107645A3 (fr
Inventor
Xingwu Wang
Michael L. Weiner
Original Assignee
Technology Innovations, Llc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US11/042,219 external-priority patent/US20060163160A1/en
Application filed by Technology Innovations, Llc filed Critical Technology Innovations, Llc
Publication of WO2005107645A2 publication Critical patent/WO2005107645A2/fr
Publication of WO2005107645A3 publication Critical patent/WO2005107645A3/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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

Definitions

  • the present invention generally relates to an apparatus for storing molecular hydrogen. More particularly, the present invention relates to a hydrogen storage device comprised of halloysite rods.
  • Carbon nanofibers including single- walled carbon nanotubes (SWNTs), multiwall nanotubes (MWNTs), and graphite nanofibers (GNF), have shown promise for applications in hydrogen storage due to the electronic nature resulting of sp 2 hybridization, large surface areas, and molecular sized pores.”
  • SWNTs single- walled carbon nanotubes
  • MWNTs multiwall nanotubes
  • GNF graphite nanofibers
  • an apparatus for storing hydrogen which is comprised of molecular hydrogen, halloysite rods, and a supporting substrate wherein hydrogen is stored within the lumen of the halloysite rods.
  • the technique and apparatus described herein is advantageous because it is inexpensive and substantially simpler compared to other approaches described in the prior art.
  • Figure 1 is a Scanning Electron Microscopy (SEM) image of a sample of halloysite
  • Figure 2A is a perspective view of a single halloysite rod while Figure 2B is an end view of the same rod
  • Figure 3 is a schematic illustration of a multiplicity of halloysite rods disposed on a substrate
  • Figure 4 is a perspective view of a substrate with halloysite rods disposed on the substrate
  • Figures 5A, 5B and 5C are perspective views of three tubular substrates with halloysite rods disposed thereon
  • Figure 6 is a schematic view of a substrate with halloysite rods disposed within a sealed storage container
  • Figure 7 is a schematic view of a plurality of substrates with halloysite rods disposed within a sealed storage container
  • Figure 8 is a flow diagram of one process of the invention
  • Figure 9 is a Scanning Electron Microscopy (SEM) image of a sample of halloysite
  • Figure 2A is a
  • FIG. 1 is a Scanning Electron Microscopy (SEM) image of a sample of halloysite 100.
  • SEM Scanning Electron Microscopy
  • halloysite may exist in a variety of morphologies, including spherical agglomerates and tubular rods.
  • the present invention utilizes the tubular halloysite rods as a hydrogen storage device.
  • halloysite 100 is comprised of halloysite rod 102 and halloysite agglomerate 104.
  • Figure 2A is a perspective view of a single halloysite rod 200 and Figure 2B is an end view of halloysite rod 200.
  • Halloysite rod 200 is comprised of lumen 202.
  • molecular hydrogen may be disposed in lumen 202.
  • halloysite rod 200 may function as a hydrogen storage apparatus in a manner similar to the hydrogen storage capability of carbon nanotubes.
  • the length 204 of halloysite rods such as 200 vary from about 100 nm to about 1 ⁇ m or more.
  • TEM Transmission Electron Microscopy
  • TEM Transmission Electron Microscopy
  • the inside diameter 208 of halloysite rods ranges from about 0.02 to about 0.04 microns and outside diameter 206 varies from about 0.04 to about 0.08 microns.
  • the term "aspect ratio" refers to the ratio of the length 204 to the outside diameter 206.
  • halloysite rods are selected which have an aspect ratio of from about 1 to about 10.
  • halloysite rods are selected which have an aspect ratio of from about 2 to about 8.
  • halloysite rods are selected which have an aspect ratio of from about 3 to about 10.
  • Figure 2 also illustrates another property of halloysite rods: their surface to volume ratio.
  • the hollow lumen of the rods provides a high surface to volume ratio.
  • the halloysite rods have a surface to volume ratio of about 1 to about 10,000.
  • the halloysite rods have a surface to volume ratio of about 10 to about 1 ,000.
  • the outer diameter 206 of halloysite rods is about 50 nm
  • the inner diameter 208 is about 20 nm
  • the length may vary from about 200 to about 500 nm. In other embodiments, the length of the rod may be as long as several micrometers.
  • Figure 3 is a schematic illustration of a multiplicity of halloysite rods 300, 302 and 304 disposed on a substrate 306.
  • rods 300, 302 and 304 have different aspect ratios.
  • at least about 80 weight percent of the halloysite rods have substantially the same aspect ratio.
  • the aspect ratio varies such that at least about 80 weight percent of the halloysite rods have an aspect ratio from about 3 to about 10.
  • at least about 80 weight percent of the halloysite rods have an aspect ratio from about 5 to about 8.
  • halloysite agglomerate 308 is also disposed on the surface of substrate 306.
  • the halloysite sample is comprised of at least about 30 weight percent halloysite rods and the remainder of the halloysite consists essentially of halloysite agglomerates.
  • the halloysite sample is comprised of at least about 50 weight percent halloysite rods.
  • the halloysite sample is comprised of at least about 60 weight percent halloysite rods.
  • Figure 4 is a perspective view of a substrate with halloysite rods disposed thereon. In the embodiment depicted, substrate 306 is coated with halloysite rods 400, 402, 406 and 408.
  • halloysite rods 400 to 408 need not be parallel to one another, nor do they need to be parallel to the surface of substrate 306.
  • halloysite rod 408 is not parallel to the surface of substrate 306.
  • halloysite agglomerate 308 is disposed on the surface of substrate 306 .
  • substrate 306 is flexible, and can be folded into a tube or cylinder.
  • Figures 5A, 5B and 5C illustrate three embodiments wherein substrate 306 is - sufficiently flexible to be folded into a tube or cylinder. In the embodiment depicted in Figure 5A, the outer surface of flexible substrate 306 has been coated with halloysite rods 500.
  • FIG. 5B the inner surface of flexible substrate 306 has been coated with halloysite rods 500.
  • both the inner and outer surface of flexible substrate 306 has been coated with halloysite rods 500.
  • Figure 6 is a schematic view of one hydrogen storage apparatus of the present invention.
  • the hydrogen storage apparatus 600 is comprised of flexible substrate 306 which, in the embodiment depicted, has halloysite rods 500 disposed on the surface thereof.
  • Flexible substrate 306 has been folded into a tubular or cylindrical shape.
  • Substrate 306 and halloysite rods 500 are disposed within sealed storage container 602.
  • Storage container 602 is sealed such that it is substantially air-tight.
  • FIG. 7 is a schematic view of another hydrogen storage apparatus of the present invention.
  • the hydrogen storage apparatus 700 is similar to apparatus 600 depicted in Figure 6 except in that a plurality of substrates 306 are employed.
  • Figure 8 is a flow diagram of one process 800 of the invention. In step 802 of process 800, halloysite rods are obtained. Not all samples of halloysite are identical.
  • Figure 9 illustrates the XRD (X-ray Diffraction) patterns of two samples of naturally occurring halloysite samples: Halloysite AZ Mill (from Halloysite S.E.
  • AZ samples contained more halloysite than the CA samples, as illustrated by the sharper and more intense peaks seen in Figure 9.
  • the AZ halloysite sample contained less than about 10 volume percent rods.
  • the CA halloysite sample contained fewer rods than the AZ sample.
  • procedures exist that allow one to synthesize halloysite in the laboratory Reference may be had to United States patent 4,098,676 to Robson (Synthetic Halloysites as Hydrocarbon Conversion Catalysts).
  • step 802 is comprised of the step of using electrostatic techniques to select halloysite rods.
  • centrifugal techniques are used.
  • a simple filtering technique is used wherein the small agglomerates are removed, thus increasing the percentage of rods.
  • the halloysite rods are obtained by synthesizing the rods.
  • the density difference between halloysite rods and halloysite agglomerates is exploited, and the halloysite is disposed in an appropriate liquid with the desirable density.
  • electrostatic techniques are used to select the halloysite rods.
  • Yuri M. Lvov entitled “Nanofabrication of ordered multilayers by alternate adsorption of polyions, nanoparticles and proteins: From planer films to microtemplates.” [online], [retrieved on 2005-03-27].
  • a positively charged substrate is brought into the proximity of a crude halloysite sample. The negatively charged particles of halloysite are attracted to the positively charged substrate.
  • centrifugal techniques are used to select the halloysite rods.
  • centrifugation is a well known technique that separates particles and solutions based on a variety of factors, including particle density, density of the supporting media, particle shape, and particle mass. A wide variety of centrifugation techniques have been developed to separate particulates.
  • continuous flow centrifugation is used to separate large quantities of halloysite rods from crude halloysite.
  • rods are selected by first placing the crude halloysite within a media of a selected density. Those halloysite particles with a density substantially similar to the density of the media will be buoyant and are thus easily isolated from the particles wherein the density is not substantially similar. Similar technology is well known to those skilled in the art. Reference may be had to United States patent 4,547,286 to Hsiung (Water Filtration Process and Apparatus Having Upflow Filter with Buoyant Filter Media and Downflow Filter with Nonbuoyant Filter Media), the content of which is hereby incorporated by reference into this specification.
  • Similar buoyancy based separation may be combined with centrifugation techniques. Such techniques are often referred to as equilibrium centrifugation or gradient centrifugation and utilize CsCI as the media. Any of the aforementioned techniques may be used to select halloysite rods of a specified morphology, for example, a certain aspect ratio. In one embodiment, halloysite rods are selected which have an aspect ratio of from about 1 to about 10. In another embodiment, halloysite rods are selected which have an aspect ratio of from about 2 to about 8. In yet another embodiment, halloysite rods are selected which have an aspect ratio of from about 3 to about 10.
  • the rods are coated onto a supporting substrate in step 804.
  • this substrate may be a flexible substrate.
  • the flexible substrate is stainless steel.
  • the substrate is a flexible polymeric substrate.
  • the flexible polymeric substrate is a polyanionic substrate. Methods for coating halloysite into polyanionic substrate are known. Reference may be had to the aforementioned paper by Yuri M.
  • the next step is the immersion of the polycation covered substrate into a dilute dispersion of polyanion or negatively charged nanoparticles (or any other nanosized charged species) also for a time optimized for the adsorption of a monolayer, then rinsed and dried.
  • These operations complete the self-assembly of a polyelectrolyte monolayer and monoparticulate layer sandwich unit onto the substrate...Subsequent sandwich units are self-assembled analogously.”
  • the same paper also discloses that "At pH above 4 halloysite is negatively charged” and may thus serve as a "nanosized charged species.”
  • a variety of polycations may be used to facilitate the binding of anionic halloysite to the substrate.
  • Lvov provided a variety of substrates with halloysite attached.
  • Lvov provided both monolayered halloysite (thickness of approximately 54 ⁇ 5 nm) and multilayered (thickness of approximately 720 nm) halloysite.
  • a sealed storage container is formed about the substrate(s) in step 806.
  • the sealed storage container is formed about a single coated substrate (see Figure 6).
  • the sealed storage container is formed about a plurality of coated substrates (see Figure 7).
  • the sealed storage container is formed prior to step 804.
  • hydrogen is stored within the lumen of the halloysite rods.
  • This storage may be effected by conventional means such as, e.g., the processes used to store hydrogen in carbon nanotube assemblies.
  • Reference may be had, e.g., to United States patents 6,159,538 to Rodriguez (Method For Introducing Hydrogen Into Layered Nanostructures); 6,672,077 to Bradley (Hydrogen Storage In Nanostructure With Physisorption); 6,596,055 to Cooper (Hydrogen Storage Using Carbon-Metal Hybrid Compositions); 6,591 ,617 to Wolfe (Method And Apparatus For Hydrogen Storage And Retrieval); 6,290,753 to Maeland (Hydrogen Storage In Carbon Material); 6,517,800 to Cheng (Production Of Single-Walled Carbon Nanotubes By a Hydrogen Arc Discharge Method) ; 6,294,142 to Nazri (Hydrogen Storage Systems and Method of Making Them); and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne un appareil destiné au stockage d'hydrogène, qui est constitué d'hydrogène moléculaire, de tiges d'halloysite, et d'un substrat de support, l'hydrogène étant stocké dans la lumière des tiges d'halloysite.
PCT/US2005/011473 2004-04-05 2005-04-05 Appareil de stockage d'hydrogene constitue d'halloysite WO2005107645A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US55955504P 2004-04-05 2004-04-05
US60/559,555 2004-04-05
US11/042,219 2005-01-25
US11/042,219 US20060163160A1 (en) 2005-01-25 2005-01-25 Halloysite microtubule processes, structures, and compositions

Publications (2)

Publication Number Publication Date
WO2005107645A2 true WO2005107645A2 (fr) 2005-11-17
WO2005107645A3 WO2005107645A3 (fr) 2009-04-30

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4364857A (en) * 1981-01-12 1982-12-21 Chevron Research Company Fibrous clay mixtures
US6159538A (en) * 1999-06-15 2000-12-12 Rodriguez; Nelly M. Method for introducing hydrogen into layered nanostructures
US6589312B1 (en) * 1999-09-01 2003-07-08 David G. Snow Nanoparticles for hydrogen storage, transportation, and distribution
US6591617B2 (en) * 2001-08-22 2003-07-15 Lockheed Martin Corporation Method and apparatus for hydrogen storage and retrieval
US6672077B1 (en) * 2001-12-11 2004-01-06 Nanomix, Inc. Hydrogen storage in nanostructure with physisorption

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4364857A (en) * 1981-01-12 1982-12-21 Chevron Research Company Fibrous clay mixtures
US6159538A (en) * 1999-06-15 2000-12-12 Rodriguez; Nelly M. Method for introducing hydrogen into layered nanostructures
US6589312B1 (en) * 1999-09-01 2003-07-08 David G. Snow Nanoparticles for hydrogen storage, transportation, and distribution
US6591617B2 (en) * 2001-08-22 2003-07-15 Lockheed Martin Corporation Method and apparatus for hydrogen storage and retrieval
US6672077B1 (en) * 2001-12-11 2004-01-06 Nanomix, Inc. Hydrogen storage in nanostructure with physisorption

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