US20070178310A1 - Non-woven fibrous materials and electrodes therefrom - Google Patents

Non-woven fibrous materials and electrodes therefrom Download PDF

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Publication number
US20070178310A1
US20070178310A1 US11/345,188 US34518806A US2007178310A1 US 20070178310 A1 US20070178310 A1 US 20070178310A1 US 34518806 A US34518806 A US 34518806A US 2007178310 A1 US2007178310 A1 US 2007178310A1
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carbon fiber
woven fibrous
population
activated carbon
fibrous material
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US11/345,188
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Rudyard Istvan
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NanoCarbons LLC
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Rudyard Istvan
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Priority to US11/345,188 priority Critical patent/US20070178310A1/en
Priority to KR1020087021383A priority patent/KR101299085B1/ko
Priority to RU2008130668/04A priority patent/RU2429317C2/ru
Priority to MX2008009821A priority patent/MX2008009821A/es
Priority to JP2008553215A priority patent/JP5465882B2/ja
Priority to AU2006337690A priority patent/AU2006337690A1/en
Priority to PCT/US2006/003964 priority patent/WO2007091995A2/en
Priority to ES06849690T priority patent/ES2725724T3/es
Priority to UAA200809938A priority patent/UA94083C2/uk
Priority to BRPI0621060-0A priority patent/BRPI0621060A2/pt
Priority to CA002637667A priority patent/CA2637667A1/en
Priority to KR1020137013539A priority patent/KR20130062380A/ko
Priority to HUE06849690A priority patent/HUE043436T2/hu
Priority to CN200680052104A priority patent/CN101626890A/zh
Priority to EP06849690.0A priority patent/EP1981705B1/en
Publication of US20070178310A1 publication Critical patent/US20070178310A1/en
Priority to IL193048A priority patent/IL193048A0/en
Priority to US13/109,702 priority patent/US8580418B2/en
Assigned to NANOCARBONS LLC reassignment NANOCARBONS LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ISTVAN, RUDYARD L.
Priority to JP2013210078A priority patent/JP5793547B2/ja
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/016—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the fineness
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D21H13/50—Carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D04H1/4242—Carbon fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02E60/13—Energy storage using capacitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer

Definitions

  • the present invention relates to fibrous materials composed of activated carbon fibers and to methods for their preparation.
  • the activated carbon fibers may be used in all manner of devices that contain activated carbon materials, including but not limited to various electrochemical devices (e.g., capacitors, batteries, fuel cells, and the like), hydrogen storage devices, filtration devices, catalytic substrates, and the like.
  • Electric double layer capacitor designs rely on very large electrode surface areas, which are usually made from “nanoscale rough” metal oxides or activated carbons coated on a current collector made of a good conductor such as aluminum or copper foil, to store charge by the physical separation of ions from a conducting electrolyte salt into a region known as the Helmholtz layer.
  • This Helmholtz layer which forms for a few Angstroms beyond the electrode surface, typically corresponds to the first two or three molecules from the surface.
  • There is no distinct physical dielectric in an EDLC which is provided instead by the electromagnetically determined Helmholtz layer. Nonetheless, capacitance is still based on a physical charge separation across an electric field.
  • Electrodes on each side of the cell store identical but opposite ionic charges at their surfaces while the electrolyte between them (but beyond the Helmholtz layer) is depleted and, in effect, becomes the opposite plate of a conventional capacitor, this technology is called electric double layer capacitance.
  • the electrodes are physically separated by a porous thin film spacer similar to electrolytic capacitors or lithium ion batteries.
  • Present EDLCs have frequency response (response curve or RC) constants ranging from milliseconds to seconds.
  • commercial EDLCs sometimes called ultracapacitors
  • EDLC carbon surface pore size should be at least about 1-2 nm for an aqueous electrolyte or about 2-3 nm for an organic electrolyte to accommodate the solvation spheres of the respective electrolyte ions in order for the pores to contribute surface available for Helmholtz layer capacitance. Pores also should be open to the surface for electrolyte exposure and wetting, rather than closed and internal. At the same time, the more total open pores there are just above this threshold size the better, as this maximally increases total surface area. Substantially larger pores are undesirable because they comparatively decrease total available surface. Research by others has shown that capacitance improves as average pore size increases from about 4 to about 20 nm
  • Compaction loss is the difference (in F/g, F/cc, or percent) between the intrinsic capacitance of a carbon and the traditional specific capacitance of a somehow formed electrode used as the metric in the industry. Industry experts guesstimate compaction loss ranging from a low of about 30% to over 80%. The actual figure will also vary with electrode thickness for any given material.
  • Compaction losses originate from at least five separate phenomena.
  • random packing of particles of differing sizes results in highly variable material voids.
  • Such voids are at best long and tortuous, and at worst completely cut off from electrolyte by random restrictions (unwetted surface).
  • the present inventor has found that the performance of EDLCs can also be increased using a fibrous material formed from a mixture of (a) 50 to 95+% of a first population activated carbon fiber fragments and (b) a second population of carbon fiber fragments of substantially similar or equal diameter to the first population and of longer length than the first population.
  • FIG. 1 is a graph depicting the final volume fractions ⁇ for the amorphous packings as a function of aspect ratio ⁇ .
  • the inset shows a magnified view of the same graph at low aspect ratio. Graph reproduced from Physical Review E 67 051301, 051301-5 (2003).
  • reaction loss refers to the difference (in F/g, F/cc, or percent) between the intrinsic capacitance of a total effective carbon surface and the traditional measured specific capacitance.
  • intrinsic capacitance refers to the ideal capacitance of the total effective carbon surface when fully double layered.
  • mesoporous as used in reference to a carbon fiber or fiber describes a distribution of surface feature pore sizes wherein at least about 20% of the total pore volume has a size from about 2 to about 50 nm.
  • catalytically-activated refers to its pore-containing surface wherein the pores have been introduced by a catalytically controlled activation (e.g., etching) process.
  • metal oxide particles of a chosen average size serve as suitable catalysts and a least a portion of the metal oxides remain in or on the fibers after the activation process.
  • fiber used in reference to polymers and carbon refers to filamentous material of fine diameter, such as diameters less than about 20 microns, and preferably less than about 10 microns, such as the type that may be obtained using conventional spinning processes.
  • nanofiber used in reference to polymers and carbon refers to a filamentous material of very fine diameter less than 1 micron, and preferably nanoscale (100 nanometers or less in diameter), such as the type that may be obtained using an electrospinning process.
  • Carbon fibers embodying features of the present invention can be prepared by any known process.
  • carbon fibers are prepared by polymerizing a monomer to form a polymer fiber and carbonizing at least a portion of the polymer fiber to provide a carbon fiber.
  • Carbon fibers can be activated using any known methods. For example, Kyotani, Carbon, 2000, 38: 269-286, have summarized available methods for obtaining mesoporous carbon fibers. Hong et al., Korean J. Chem. Eng., 2000, 17(2), 237-240, described a second activation of previously activated carbon fibers by further catalytic gasification. Preferred methods for preparing carbon fibers with controlled mesoporosity are described in U.S. application Ser. No. 11/211,894, filed Aug. 25, 2005; the entire contents of that application are incorporated herein by reference. Ideally, one should control the activation of the carbon fiber to ensure mesopore formation, as described in U.S. application Ser. No. 11/211,894. However, activated carbon fibers formed from other methods of preparation can also be used in this invention.
  • the activated carbon fibers of the present invention comprise diameters of about 10 microns or less, in other embodiments of about 5 microns or less, in other embodiments of about 1 micron or less, in other embodiments of about 500 nm or less, in other embodiments of about 100 nm or less.
  • the preferable diameter depends on the process used to create the fibrous material.
  • the activated carbon fibers of the present invention have pores (i.e. they are not smooth surfaces).
  • the size of pores introduced on the fiber surfaces and into the fibers during activation depends on the process, and a preferred embodiment is the catalytic activity of a nanoparticulate metal oxide catalyst, its amount, and/or the size of its nanoparticles as well as the conditions of activation. In general, it is desirable to select pore sizes large enough to accommodate the particular electrolyte used to an optimal surface packing but substantially larger in order to prevent unnecessary reductions in total fiber surface area.
  • the average pore size typically ranges from about 1 nm to about 20 nm. Ideally, the average pore size is from about 3 nm to 15 nm, preferably 6-10 nm.
  • the present invention is based on the realization that a reasonably homogenous population of rod-shaped fragments of carbon fibers can be used to maximize both the surface area and the porosity of a fibrous material formed therefrom.
  • a first surprising aspect of the invention is that both mathematical models and experimental evidence show that low ⁇ fibrous materials (short rods, cylinders, or fibers) can randomly back as densely as spheres.
  • the theoretical three dimensional random packing limit for spheres is 0.64, known as the Bernal limit. Empirically, the Bernal limit is measured at about 0.63 due to inhomogeneous experimental materials.
  • cylinders with aspect ratio ⁇ of 2 have a packing density ⁇ of about 0.62.
  • a regular number of contacts on longer conducting elements with reduced numbers of total grain boundaries through the material to the collector foil improves electrical conduction and reduces ESR.
  • the long narrow void channels in cylinder packings have electrolyte diffusion and ionic conductivity advantages, similar to carbon fiber cloth, but without the same material density limitations and at lower cost since the weaving step is avoided.
  • Ordinary carbon papers or felts are comprised of a highly polydisperse aspect ratio distribution of mostly longer fibers that cannot achieve the same random packing density and total surface.
  • the expense of manufacturing fiber is rationalized by using its length (for example, for tensile strength or conductive continuity).
  • the present invention proposes to take advantage only of the cylindrical geometry in short lengths. Since these random packing properties are scale invariant, they can be predictably extended to a second generation of finer fibrous materials.
  • carbon fibers can fragment.
  • the fibers are further fragmented so that the average length of the fibers is relatively homogenous.
  • Fibers can be fragmented using any know means such as chemical or mechanical milling, and screened by means such as advanced air classifiers into particle distributions without excessive polydispersion, for example a distribution of aspect ratios from 1 to 5 but concentrated within 2 to 3.
  • a typical commercial activated carbon particulate dispersion is from 3 to 30 microns with a median of 8 microns; it is highly polydisperse. The many smaller particles are meant to fit into the voids between the fewer large ones to maximize total surface, but giving rise to compaction loss.
  • the carbon fibers embodying features of the present invention may be broken up into shorter fragments (e.g., after carbonization and during or after activation) and then applied to a substrate (e.g., as a slurry) to form a non-woven paper-like layer.
  • a particulate-like short fiber fragment powder may be made from the bulk longer material by crushing, milling, chopping, grinding, chemical milling, etc., with an engineered fragment length distribution for subsequent coating onto a substrate (e.g., an electrode surface).
  • the population of fragments for maximal random packing has an average length of one to five times the diameter; that is an aspect of 1 to 5.
  • Aspect ratios less than 1 constitute fines that can “clog” material pores; higher aspect ratios do not pack as densely.
  • An aspect ratio can be selected for a specific device characteristic; for example, for power density more material porosity is desirable to enable electrolyte mass transport (higher ratio), while for energy density more surface from a denser packing might be desirable (lower ratio).
  • milling and screening processes result in a particle distribution with some dispersion around the engineering design goal.
  • a practical minimum average length is envisioned. In some embodiments as with 7 micron diameter fiber this length may be 15 micron at an aspect ration around two. In some embodiments with 5 micron diameter fibers it may be 10 micron length also at aspect ratio 2. For electrospun nanofibers below one micron in diameter, a preferred length may remain a few microns for conductivity, resulting in aspect ratios that increase as fiber diameter decreases.
  • FIG. 1 shows theoretical and experimental results for monodisperse packings (taken from Physical Review E27 051301 (2003).
  • the aspect ratio distribution of the resulting fibrous powder will result in a material of predictable average density and porosity according to these principles of random packing.
  • the first population would comprise fragments with reasonably homogenous lengths and diameters.
  • Other populations of activated fiber fragments would contain substantially the same diameter as the first population, but would have longer lengths and higher aspect ratios.
  • the heterogeneous mixture contains from about 50 to 95% of a first population of substantially homogenous (not highly polydisperse) fragments and the balance fragments of substantially similar diameter to the first population, but with longer lengths.
  • the length of the fibers in the second population is greater than about twice the length of the first population, in another embodiment the second population is five times as long. In another embodiment, the longer fibers are 50, 100, 150, or 200 microns in average length irrespective of the first population, said lengths corresponding to the desired average thickness of the electrode material.
  • the fibers of the present invention can be further processed to provide a material according to the present invention compatible with conventional particulate carbon coating processes as described in U.S. Pat. Nos. 6,627,252 and 6,631,074, the entire contents of both of which are incorporated herein by reference, except that in the event of any inconsistent disclosure or definition from the present application, the disclosure or definition herein shall be deemed to prevail.
  • the density of the resulting “paper-like” fibrous material is an engineered property of the length of the fiber fragments compared to their diameter (their aspect ratio), the polydisperse distribution of the lengths compared to the average diameter, and optionally post deposition densification (e.g. by pressure). If length approaches diameter, then the fragments will be more like conventional particles and pack more densely with less porosity in the resulting material. If length is much larger than diameter, then the aspect ratio will be high and packing less dense (i.e. a more porous void to volume ratio material).
  • the average aspect ratio of length to diameter may be adjusted and/or blends of different ratios may be used to provide any material porosity (void/volume ratio) desired within the limits of random packing principals.
  • at least about 50% of the total number of carbon fiber fragments have a length ranging from about 5 to about 30 microns equivalent to some activated carbon particulate materials.
  • at least about 50% of the total number of fragments has aspect ratios lower than 30.
  • average aspect ratios are lower than 20.
  • average aspect ratios are lower than 10.
  • the fiber fragment diameters at or below 100 nm more closely resemble carbon nanotubes at least about 50% of the total number of carbon fiber fragments are less than 1 micron in length with aspect ratios less than 20.
  • EDLC electrodes are typically made of activated carbon bonded directly or indirectly onto a metal foil current collector, although metal oxides can be used.
  • activated carbon materials prepared by the methods described herein may be applied to current collectors together with additional metal oxides or the like for hybrid characteristics including enhanced pseudocapacitance.
  • a capacitor embodying features of the present invention includes at least one electrode of a type described herein.
  • the capacitor further comprises an electrolyte, which in some embodiments is aqueous, in other embodiments is organic.
  • the capacitor exhibits electric double layer capacitance.
  • the capacitor particularly when residual metal oxide is present on the surface of the activated carbon fibrous material, the capacitor further exhibits pseudocapacitance.
  • organic electrolytes have lower conductivity than aqueous electrolytes, they have slower RC characteristics and higher ESR contributions, and reach mass transport pore restrictions at substantially larger geometries since they are much larger solvated ions. However, since they have breakdown voltages above 3 V compared to 1 V with aqueous electrolytes, organics produce higher total energy density since total energy is a function of voltage squared. Carbon pores and materials optimized for organics would optionally work for aqueous electrolytes also, since aqueous solvation spheres are smaller. This would allow, for example, ultracapacitor devices to be tailored to RC requirements irrespective of carbon manufacture by changing the electrode packing density via aspect ratio, and by changing electrolyte.
  • Hybrid devices would naturally have a wider range of total RC characteristics since they combine the EDLC with the PC capacitive phenomena.
  • the practical range for use in hybrid electric vehicles is less than about one second to over about 15 seconds, and for distributed power less than about 0.01 seconds to over about 1 second.
  • Activated mesoporous carbon fibers or fibers, or their respective fragments, embodying features of the present invention may be incorporated into all manner of devices that incorporate conventional activated carbon materials or that could advantageously be modified to incorporate fibrous carbon materials of engineered material geometry, surface, porosity, and conductivity.
  • Representative devices include but are not limited to all manner of electrochemical devices (e.g., capacitors; batteries, including but not limited to one side of a nickel hydride battery cell and/or both sides of a lithium ion battery cells; fuel cells, and the like). Such devices may be used without restriction in all manner of applications, including but not limited to those that potentially could benefit from high energy and high power density capacitors or the like.

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US11/345,188 US20070178310A1 (en) 2006-01-31 2006-01-31 Non-woven fibrous materials and electrodes therefrom
BRPI0621060-0A BRPI0621060A2 (pt) 2006-01-31 2006-02-03 materiais fibrosos não-tecidos e eletrodos do mesmo
CA002637667A CA2637667A1 (en) 2006-01-31 2006-02-03 Non-woven fibrous materials and electrodes therefrom
MX2008009821A MX2008009821A (es) 2006-01-31 2006-02-03 Materiales fibrosos no tejidos y electrodos a partir de estos.
JP2008553215A JP5465882B2 (ja) 2006-01-31 2006-02-03 不織繊維材料及びそれから作られる電極
AU2006337690A AU2006337690A1 (en) 2006-01-31 2006-02-03 Non-woven fibrous materials and electrodes therefrom
PCT/US2006/003964 WO2007091995A2 (en) 2006-01-31 2006-02-03 Non-woven fibrous materials and electrodes therefrom
ES06849690T ES2725724T3 (es) 2006-01-31 2006-02-03 Materiales fibrosos y electrodos de los mismos
UAA200809938A UA94083C2 (uk) 2006-01-31 2006-02-03 Нетканий волокнистий матеріал (варіанти) та електроди, виготовлені з нього
KR1020087021383A KR101299085B1 (ko) 2006-01-31 2006-02-03 부직포 재료 및 부직포 재료로 제조한 전극
RU2008130668/04A RU2429317C2 (ru) 2006-01-31 2006-02-03 Нетканые волокнистые материалы и электроды из них
KR1020137013539A KR20130062380A (ko) 2006-01-31 2006-02-03 부직포 섬유 재료 및 이로 제조한 전극
HUE06849690A HUE043436T2 (hu) 2006-01-31 2006-02-03 Rostos anyagok és azokból készült elektródák
CN200680052104A CN101626890A (zh) 2006-01-31 2006-02-03 无纺纤维质材料以及从其得到的电极
EP06849690.0A EP1981705B1 (en) 2006-01-31 2006-02-03 Fibrous materials and electrodes therefrom
IL193048A IL193048A0 (en) 2006-01-31 2008-07-24 Non-woven fibrous materials and electrodes therefrom
US13/109,702 US8580418B2 (en) 2006-01-31 2011-05-17 Non-woven fibrous materials and electrodes therefrom
JP2013210078A JP5793547B2 (ja) 2006-01-31 2013-10-07 活性炭素繊維の断片を含む繊維材料及びそれから作られる電極

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AU (1) AU2006337690A1 (ja)
BR (1) BRPI0621060A2 (ja)
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US20080254972A1 (en) * 2007-02-14 2008-10-16 Rudyard Lyle Istvan Methods of forming activated carbons
US20090246528A1 (en) * 2006-02-15 2009-10-01 Rudyard Lyle Istvan Mesoporous activated carbons
US20110220393A1 (en) * 2006-01-31 2011-09-15 Rudyard Istvan Non-woven fibrous materials and electrodes therefrom
WO2012175997A3 (en) * 2011-06-22 2013-03-21 Acal Energy Ltd Cathode electrode material
US20150116905A1 (en) * 2013-10-24 2015-04-30 Corning Incorporated Ultracapacitor with improved aging performance
WO2015095902A1 (de) 2013-12-23 2015-07-02 Lenzing Ag Verfahren zur herstellung von carbonpartikeln
CN106605326A (zh) * 2015-07-24 2017-04-26 住友电气工业株式会社 氧化还原液流电池用电极、氧化还原液流电池和电极的特性评价方法
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