WO2001066217A1 - Electrodes de faible volume poreux a condensateur de recyclage et utilisation de stockage d'energie et procede - Google Patents

Electrodes de faible volume poreux a condensateur de recyclage et utilisation de stockage d'energie et procede Download PDF

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Publication number
WO2001066217A1
WO2001066217A1 PCT/US2001/007295 US0107295W WO0166217A1 WO 2001066217 A1 WO2001066217 A1 WO 2001066217A1 US 0107295 W US0107295 W US 0107295W WO 0166217 A1 WO0166217 A1 WO 0166217A1
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WIPO (PCT)
Prior art keywords
electrode
pore volume
less
carbon
capacitor
Prior art date
Application number
PCT/US2001/007295
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English (en)
Inventor
Marc D. Andelman
Original Assignee
Andelman Marc D
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.)
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4691Capacitive deionisation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/46109Electrodes
    • C02F2001/46152Electrodes characterised by the shape or form
    • C02F2001/46157Perforated or foraminous electrodes
    • C02F2001/46161Porous electrodes

Definitions

  • Carbons may take the form of fibers, powders, aerogels, or nanotubes. Pore volume comes associated with the surface area necessary for high capacitance, high performance electrodes. This pore volume gets larger directly proportional to the amount of macro versus meso and micropores. Lowering the surface area lowers the pore volume, but, for a given material, also lowers capacitance. Between electrode materials, selecting for a preponderance of micro and meso versus macropores allows for more useful surface area.
  • BET Brunauer Emmett Teller method
  • U.S. Patent No. 5,150,283 describes metal foil current collectors with activated carbon attached by binders. Selecting these activated carbons for low pore volumes, e.g., below 1 cc/gram, and preferably, below .8 cc/gram would suit the purposes of this invention.
  • metal foils tend to corrode and also have a high Schottky barrier, which causes a contact resistance intrinsic to the dissimilar carbon and metal materials .
  • a graphite foil current collector would overcome this problem when used as an integral, current collector bonded with similar carbon-containing active electrode materials.
  • U.S. Patent No. 5,620,597, issued April 15, 1997 shows such an electrode in Figs.
  • the invention relates to a low pore volume electrode, flow-through capacitor and energy storage use and method. Therefore, an electrode with a low pore volume, capacitance- containing active layer would be desirable for use in a flow- through capacitor.
  • the capacitance-containing active layer is the material layer which contains most of the capacitance.
  • this electrode should contain an integral current collector bonded to the active, high capacitance electrode layers.
  • This current collector should preferably be matched to the materials used in the active, high capacitance, low pore volume electrode layers, such as carbon-containing active layers and graphite foil current collectors. Such an electrode would also be useful in an energy storage capacitor. In order to achieve this, a low pore volume electrode material is desirable.
  • Such a material may be any surface area material. Typically, such a material will be between 100 square meters per gram and 3000 square meters per gram. These materials need to be selected for pore volumes that are 1 cc/gram or less, preferably, 0.8 cc/gram or less.
  • the low pore volume, high capacitance material may be bonded to an integral current collector or it should have an integral current collector bonded to it.
  • the current collector should be thin, so as not to take up excessive space. Ideally, it should be between 0.0001 and 0.1 inches thick, preferably 0.001 to 0.03 inches thick.
  • the invention comprises a low pore volume electrode material wherein less than 50% of its pore volume comprises macropores, with a capacitance-containing active layer bonded to an integral current collector. This is an electrical bond which may be made by compression, mechanical or chemical means .
  • the current collector which may be a film material, may be any conductive metal, conductive polymer, composite, carbon material filled into a polymer, or conductive ceramic material.
  • Graphite foil is a preferred embodiment, because it is a close materials match to preferred carbonaceous high capacitance materials used that comprise the active electrode layers. Therefore, graphite has a low Schottky barrier and a low junction resistance with the preferred carbon-containing materials including: graphite; glassy carbon, carbon particles; fiber; carbon aerogel; carbon foam; nanotube; or aligned nanotube, active electrode materials.
  • One especially advantageous embodiment of the invention is the use of materials with a preponderance of micropores and mesopores compared to macropores. Macropores, as defined by.
  • a preferred embodiment is a material with greater than 30% of the pore volume representing pores with diameters of less than 50 nanometers, to enable efficient purification of concentrated solutions over 2500 ppm with such materials, typically, to provide a high capacitance to pore volume ratio, ideally, greater than 20 farads per cubic centimeter of pore volume.
  • materials with high capacitance to pore volume ratios including selected pyrolized polymers, carbon fibers, aerogels, and carbon foams are selected for pore volumes less than 1 cc/gram, and preferably 0.8 cc/gram or less.
  • the active layer be low in pore volume, so as to be useful for efficient purification, flow-through capacitors.
  • U.S. Patent No. 5,150,283 describes metal foil current collectors with activated carbon attached by binders. Selecting these activated carbons for low pore volumes, e.g., below 1 cc/gram, and preferably, below 0.8 cc/gram, would suit the purposes of this invention.
  • metal foils tend to corrode and also have a high Schottky barrier, which causes a contact resistance intrinsic to the dissimilar carbon and metal materials.
  • U.S. Patent No. 5,620,597 issued April 15, 1997, Figs.
  • such glassy carbons should have an electrode planar area capacitance of 0.2 farads/square cm or greater, and a pore volume of 0.8 cc/gram or less, a weight specific capacitance of 20 farads per gram or greater, and a volumetric capacitance of 20 farads per cc or greater, as measured in concentrated H 2 S0 4 .
  • Thickness of the glassy carbon layer, deposited upon the graphite foil current collector should be between 0.2 and 200 mils. However, for thicknesses much over 0.4 mils, surface stresses tend to crack the glassy carbon coating. To alleviate these stresses and facilitate manufacturing, it is desirable to incorporate x-y or radial grids of naked, bare electrode. This can be achieved by masking the graphite foil, applying the glassy carbon precursor on top of the mask, and pyrolyzing.
  • a low carbon-containing blocking agent for example, wax or any other ablatable compound
  • the glassy carbon precursor is painted, doctor bladed, sprayed, or otherwise deposited on top, but does not adhere to the wax or blocking agent.
  • the precursor such as, but not limited to any of the glassy carbon precursors, may include phenolic resin, furfural alcohol, mesophase pitch, polyimide, etc. Upon pyrolyzing, this blocking agent ablates away, thereby leaving a grid of naked graphite foil.
  • the grid patterns can shrink along with the overall electrode, thereby relieving stresses and preventing cracking during manufacture.
  • the graphite foil layer should be between 2 mils and 50 mils, and preferably 3 to 13 mils.
  • Fig. 1A is a top plan view of a glassy carbon electrode
  • Fig. IB is a side view of the glassy carbon electrode of Fig. 1A
  • Fig. 1A is a top plan view of a glassy carbon electrode
  • Fig. IB is a side view of the glassy carbon electrode of Fig. 1A
  • Fig. 2 is a schematic illustration composed of a nanolithic electrode of aligned nanotubes attached to a graphite foil. Description of the Embodiments
  • Figs. 1A and IB illustrate a glassy carbon electrode with embossed lines to prevent stress cracking during manufacture, which is prepared by masking and pyrolyzing or plasma etching of graphite foil.
  • high capacitance materials are conductive polymers, as described in U.S. Patent No. 5,733,683, issued March 31, 1998, and incorporated by reference.
  • these may be applied as a coating to a thin metal foil or graphite current collector.
  • the precursor is pyrolized in an oven to glassy carbon.
  • the glassy carbon is subsequently electrochemically or thermally activated to a BET level of 1000 or higher.
  • Another preferred embodiment of the invention is aligned nanotubes grown directly upon graphite foil. These may be grown in a tube furnace or by plasma CVD, and are well- described in various scientific papers, including, but not limited to: "Single Wall Nanotubes Produced by Metal Catalyzed Disproportionation of Carbon Monoxide”; Hongjie Dai et al, Chemical Physics Letters , 260, pp. 471-475; "Growth of Highly Oriented Carbon Nanotubes by Plasma-Enhanced Hot Filament Chemical Vapor Deposition”; Z.P. Huang et al, Applied Physics Letters, Volume 23, No. 2628, December 1998; “Large Arrays of Well-Aligned Carbon Nanotubes”; Z.F.
  • Fig. 2 is an illustration of aligned nanotubes grown and extending substantially perpendicularly from a graphite foil collector to provide a nanolithic electrode with an integral current collector.
  • the aligned nanotube, graphite foil collector of Fig. 2 has the flow-through capacitor or energy storage device employing nanotube-graphite foil electrodes and may have nanotubes which are hemogeneous or inhomogeneous in respect to diameter, length, material, or wall thickness.
  • the nanotubes may be subsequently treated, e.g., thermally or chemically, as to enhance surface area, such as by acid treatment.
  • One advantage of nanotubes is that the ionic conductive path is relatively straight down through the nanotubes.
  • the nanotubes may be preferentially attached more or less perpendicular to the current collector. Aligned nanotubes, as may be grown in a tube furnace, require a substrate to support the nanotube catalyst. This is shown on the Web site http: //buckv5.wustl . edu/Science/Nanofiber Growth .html .
  • the catalyst supporting substrate/current collector may be any metal foil.
  • a preferable embodiment is graphite foil, since this has a similar material composition to the nanotubes, and therefore, offers a lower Schottky barrier.
  • the catalyst may be any metal, metal-containing compound, such as: iron; nickel molybdenum; etc., that is used to catalyze the growth of nanotubes .
  • the catalyst may be applied with a mixture of phenolic resin, mesophase pitch, furfural I alcohol, or other carbon-containing adhesive mixture. This mixture is pyrolized, either prior to or during nanotube formation, thereby firmly adhering catalyst microparticles, in a carbon or glassy carbon matrix, onto the surface of the substrate material. Nanotubes formed from this adhered catalyst are better adhered to the integral current collector substrate material for optimum performance as a capacitor electrode, whether for a flow-through capacitor or energy storage use.
  • the nanotubes should be grown onto an intrinsic, integral graphite foil current collector to enhance the surface area, and therefore the capacitance, yet retain low pore volume.
  • the nanotubes should also be thin, e.g., less than 200 nm in diameter. Surface area increases exponentially with thinness, but only linearly with the length of the nanotubes. Preferentially, the nanotubes should be less than 50 nm in diameter.
  • the nanotubes may be any length up to 500 microns. However, to improve the capacitance to pore volume ratio, the nanotubes should be much thinner than taller, e.g., in a ratio of 1 to 100 or greater. For example, nanotubes 100 microns tall should be 200 nm thin or less.
  • Graphite foil 3 mils thick, is coated with glassy carbon to a thickness of between 0.2 to 10 mils, either single or double-sided coated.
  • the glassy carbon is subsequently activated by thermal oxidation until it has a surface area as measured by BET of over 1000. Pore volume is measured at 50%.
  • Capacitance is over 0.2 farads per electrode plane area square centimeter, providing for a high capacitance, low series resistance capacitor with a series resistance of less than 0.1 ohm.
  • UCAR graphite foil 3 mils thick, is coated with 20 mils of glassy carbon on each side in an x-y grid pattern, similar to the one shown in Fig.
  • the capacitor is incorporated in a PVC, box-shaped cartridge holder provided with an inlet and an outlet.
  • An oily waste mixture containing suspended oil droplets in concentrated brine of 10,000 ppm salt is passed through the capacitor at 100 mis/minute and purified to a level of 1000 ppm salt in a batch recycle loop mode. This breaks the colloidal suspension, allowing the oil droplets to coalesce together and separate from the water. The oil is then skimmed off from the water and recovered.
  • Graphite foil 5 mils thick, is coated with a mixture of an adhesive hydrogel, such as: polyvinyl alcohol; polyvinyl pyrrone; gelatin; and a nanoparticulate metal catalyst, such as molybdenum nanoparticles of less than 20 nanometers in diameter.
  • an adhesive hydrogel such as: polyvinyl alcohol; polyvinyl pyrrone; gelatin; and a nanoparticulate metal catalyst, such as molybdenum nanoparticles of less than 20 nanometers in diameter.
  • any nanoparticle colloid or nanoparticle-polyelectrolyte mixture may be applied to form a nanoparticle layer on the graphite foil.
  • the low carbon- containing hydrogels or polyelectrolytes ablate away. Aligned carbon nanotubes are grown by disproportionation of C0 2 in a tube furnace at 1200°C.
  • the resultant nanotubes are 5 nanometers in diameter and 10 microns tall, with a length to width ratio of 2000 and a BET surface area of the nanotube layer of over 800 square meters per gram, a capacitance of over 0.8 farads per square centimeter of electrode plane area surface, and over 80 farads per gram of the combined electrode current collector material.
  • Pore volume is less than 0.004 cc per each farad capacitance, and inefficiency, due to repurification of pore volume ions, is less than 20% when these electrodes are built into flow- through capacitors, according to the designs in U.S. Patent No. 5,748,437, issued May 5, 1998.
  • This electrode is made into a spiral wound, flow-through capacitor and used to purify a dilute hard water solution of 500 ppm.
  • Example 3 Graphite foil, 0.003 inches thick, is coated with a metal nanoparticle catalyst, where nanotubes are grown in a 900°C tube furnace.
  • the metal nanoparticles are deposited via ion implantation, sputtering, or onto the graphite foil substrate, in order to form especially small metal nanoparticles, e.g., under 10 nanometers, and nanotubes less than 10 nm wide, in order to produce a high capacitance, low pore volume electrode.
  • This electrode is incorporated into a 3 volt, 10 farad capacitor comprising three cells in series of 1 volt each, for use in CMOS and computer memory circuits with enhanced power usage properties, due to low electrical series resistance (ESR) of the capacitor of below 0.1 ohms.
  • ESR electrical series resistance
  • Graphite foil 0.005 inches thick, is coated with metal nanoparticle catalyst, which is applied by mixing a metal salt solution with an adhesive hydrogel, spraying it onto the graphite foil surface, and air drying.
  • metal nanopowders may be suspended in the air and electrostatically powder-coated onto the graphite foil.
  • the catalyst-coated graphite foil is put inside a 3 foot diameter tube furnace.
  • Nanotubes 2 to 40 nanometers in diameter, are grown as in inhomogeneous mixture, with lengths from 5 to 100 microns, in order to produce a high capacitance, low volume electrode with an integral, attached current collector and capacitance greater than 0.2 farads/electrode plane area square centimeter and greater than 10 farads per gram of total electrode material .
  • Graphite foil 3 mils thick, is painted with a mixture of phenolic resin and iron nitride, to form a catalyst-phenolic film layer. This is carbonized in a 1000°C oven to form a 0.0002 inch film of carbon with reduced metal nanoparticles less than 10 nm in diameter. Subsequently, the electrode formed by this process is a substrate on which to grow tightly adhered nanotubes for use as a capacitor electrode with an integral, graphite foil current collector.
  • Carbon cloth with a pore volume of 0.8 grams/cc is used with a graphite foil current collector and a compression contact to build a flat plate, flow-through capacitor. This material is used to remove 90% of the ions from tap water for a home water purification unit of 100 gallons per day, with an energy usage of 5 watt hours per gallon or less.

Abstract

Cette invention concerne une électrode de faible volume poreux dans laquelle moins de 50 % de son volume poreux comprend des macropores et dans laquelle une couche active contenant une capacité est liée à un collecteur de courant solidaire. Le matériau de l'électrode de faible volume poreux fait office de couche active et peut être constitué d'un matériau en carbone de faible volume poreux. Le collecteur de courant solidaire peut être composé d'une feuille de graphite et doit avoir une épaisseur comprise entre 0,0001 et 0,1 pouce. Cette électrode de faible volume poreux peut être utilisée dans un condensateur de recyclage pour purifier des solutions concentrées et stocker de l'énergie.
PCT/US2001/007295 2000-03-06 2001-03-05 Electrodes de faible volume poreux a condensateur de recyclage et utilisation de stockage d'energie et procede WO2001066217A1 (fr)

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US18735100P 2000-03-06 2000-03-06
US06/187,351 2000-03-06

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6515325B1 (en) * 2002-03-06 2003-02-04 Micron Technology, Inc. Nanotube semiconductor devices and methods for making the same
US6781817B2 (en) 2000-10-02 2004-08-24 Biosource, Inc. Fringe-field capacitor electrode for electrochemical device
US7666051B2 (en) 2004-07-16 2010-02-23 The Trustees Of Boston College Device and method for achieving enhanced field emission utilizing nanostructures grown on a conductive substrate
US20140202880A1 (en) * 2011-04-29 2014-07-24 The Board Of Trustees Of The Leland Stamford Junior University Segmented electrodes for water desalination
US11358883B2 (en) 2019-02-05 2022-06-14 Lawrence Livermore National Security, Llc System and method for using ultramicroporous carbon for the selective removal of nitrate with capacitive deionization

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5192432A (en) * 1990-04-23 1993-03-09 Andelman Marc D Flow-through capacitor
US5476734A (en) * 1994-04-28 1995-12-19 Westinghouse Electric Corporation Current collector with integral tab for high temperature cell
US5538611A (en) * 1993-05-17 1996-07-23 Marc D. Andelman Planar, flow-through, electric, double-layer capacitor and a method of treating liquids with the capacitor
US5620597A (en) * 1990-04-23 1997-04-15 Andelman; Marc D. Non-fouling flow-through capacitor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5192432A (en) * 1990-04-23 1993-03-09 Andelman Marc D Flow-through capacitor
US5620597A (en) * 1990-04-23 1997-04-15 Andelman; Marc D. Non-fouling flow-through capacitor
US5538611A (en) * 1993-05-17 1996-07-23 Marc D. Andelman Planar, flow-through, electric, double-layer capacitor and a method of treating liquids with the capacitor
US5476734A (en) * 1994-04-28 1995-12-19 Westinghouse Electric Corporation Current collector with integral tab for high temperature cell

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6781817B2 (en) 2000-10-02 2004-08-24 Biosource, Inc. Fringe-field capacitor electrode for electrochemical device
US6515325B1 (en) * 2002-03-06 2003-02-04 Micron Technology, Inc. Nanotube semiconductor devices and methods for making the same
US6858891B2 (en) 2002-03-06 2005-02-22 Micron Technology, Inc. Nanotube semiconductor devices and methods for making the same
US7081385B2 (en) 2002-03-06 2006-07-25 Micron Technology, Inc. Nanotube semiconductor devices and methods for making the same
US7666051B2 (en) 2004-07-16 2010-02-23 The Trustees Of Boston College Device and method for achieving enhanced field emission utilizing nanostructures grown on a conductive substrate
US20140202880A1 (en) * 2011-04-29 2014-07-24 The Board Of Trustees Of The Leland Stamford Junior University Segmented electrodes for water desalination
US11358883B2 (en) 2019-02-05 2022-06-14 Lawrence Livermore National Security, Llc System and method for using ultramicroporous carbon for the selective removal of nitrate with capacitive deionization

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