EP1171923A1 - Fibres de carbone pour batteries au graphite doubles - Google Patents

Fibres de carbone pour batteries au graphite doubles

Info

Publication number
EP1171923A1
EP1171923A1 EP01908719A EP01908719A EP1171923A1 EP 1171923 A1 EP1171923 A1 EP 1171923A1 EP 01908719 A EP01908719 A EP 01908719A EP 01908719 A EP01908719 A EP 01908719A EP 1171923 A1 EP1171923 A1 EP 1171923A1
Authority
EP
European Patent Office
Prior art keywords
carbon
carbon material
webbing
carbonaceous material
affixed
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.)
Withdrawn
Application number
EP01908719A
Other languages
German (de)
English (en)
Inventor
Lisa Marie Massaro
Thongkhanh P. Lewandowski
William Edward Orabone, Jr.
Gregory Kenneth Maclean
Sui-Yang Huang
Stephanie Lynn Kaczan
David Russell Smith
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lion Compact Energy Inc
Original Assignee
Lion Compact Energy Inc
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
Application filed by Lion Compact Energy Inc filed Critical Lion Compact Energy Inc
Publication of EP1171923A1 publication Critical patent/EP1171923A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • H01M4/96—Carbon-based electrodes
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to carbon materials for use in energy storage cells and batteries More specifically, the present invention relates to carbon materials for use in dual graphite energy storage cells and batteries
  • Carbon is used as an active material for battery electrodes for many different structures ranging from soft, amorphous carbon to hard, crystal and graphite and in many different forms such as powders and fibers Traditionally, these carbons have been bound or pasted to a metal substrate to provide an electrical path from the active material to the battery terminals
  • the materials used to bind the carbon to the metal typically interfere with the electrochemistry, add resistance to the electrode, and increase the weight of the electrode
  • Metal current collectors can contribute as much as half of the weight of a battery electrode
  • U S Patent 5,677,084 to Tsukamoto, et al discloses carbon fibers that are used in carbonaceous material in the form of a unidirectionally arranged 5 body in combination with electrically conductive fibers or foil
  • a problem disclosed in the prior art is the concern that proper conductivity occurs
  • the carbon particles or fibers were attached to a matting or adhered to an electro conducting foil, such as a metal foil to the entire carbonaceous area This provided sufficient conductivity, thereby ⁇ o enabling proper conductivity of the carbon material
  • Lithium ion secondary batteries concern the shuttling of the lithium ions from one electrode to the other (cathodes and anodes) with no direct use of anions that may be present in the system for energy storage
  • the carbon materials used in dual graphite systems are chosen with different requirements than seen in much of the prior art U S
  • Patent 5,993,997 to Fujimoto, et al describes the use of a carbon compound material capable of occluding and discharging lithium (or dop ⁇ ng/de-dop ⁇ ng) whicr is then shuttled to the negative electrode composed mainly of a carbon material that intercalates and deintercalates the lithium in opposition to the reaction occurring at the opposite electrode
  • This patent is typical of the prior art
  • the dual graphite energy storage system is very different
  • the graphites chosen for dual graphite systems are used strictly to intercalate and deintercalate both cations and anions at two different electrodes
  • the ions are strictly drawn out of the electrolyte solution for intercalation, and never from one electrode to the other
  • the cations migrate and intercalate into one electrode at the same time the anions migrate and intercalate into the other electrode
  • the reverse process also occurs simultaneously This explains why many skilled in the art refer to this technology as dual intercalating
  • the carbonaceous materials used in dual graphite systems require a unique selection
  • U S Patent 5,145,732 to Kyutoku, et al discloses the use of a carbon felt material however the material is referred to as a thermal insulator, expressing that the material is not principally conductive nor principally one of continuous carbon structure, and in addition the material is impregnated with a resin
  • Other prior art references disclose the use of a carbon aerogel for use in a battery
  • U S Patent 5,932,185 refers to the use of carbon foams as electrodes where the thickness of the electrode is less than 40 mils
  • the present invention provides a carbon material for use in a dual graphite battery
  • the carbon material includes a carbonaceous material having a Young's modulus of greater than 75MSI
  • a conductive carbon material for use in an energy storage system wherein the carbon material includes a carbonaceous material selected from the group consisting essentially of a single conductive fiber, a multiplicity of conductive fibers, conductive fibers formed into a cloth, a carbon foam and a carbon mat in which the fibers are thermally fused together
  • Included in the invention is a carbon material or fiber having a crystallite surface calculated by 1/[(Lc/d002)+1] of less than or equal to 0 025 for anion intercalation, and a method for making stabilized unidirectional cloth by affixing a webbing to a carbonaceous material
  • Figure 1 is a graph comparing the degree of graphitization of the carbon fiber tested as the as the anion intercalation/deintercalation fiber versus the anion fiber discharge capacity measured in mAh/g,
  • Figure 2 is a graph depicting the crystallite surface (as calculated by 1/((Lc/d002)+1)) versus the anion discharge capacity for various types of carbon fibers, and
  • Figure 3 is a schematic representation of various types of continuous carbon fibers that can be used in dual graphite cells and batteries from a top view, (3)(a) shows a woven material, (3)(b) shows a unidirectional material, (3)(c) shows a biaxial braid material, (3)(d) shows a tnaxial braid material, and (3)(e) shows an end result of a carbon foam or a carbon mat in which fibers are thermally fused to each other
  • the present invention provides a carbon material for use in a dual graphite battery
  • the carbon material is made of a carbonaceous material having a Young's modulus greater than 75MSI
  • the present invention uses a conductive carbon/graphite material consisting of one or more of the following
  • Energy storage is greatly enhanced by the proper selection of carbon materials Increasing the energy capacity of the anion intercalating electrode means that less volume and weight of carbonaceous material is required to achieve more energy storage This in turn increases the entire energy storage device's energy density giving the device more energy per weight and volume In addition, less total carbonaceous material in the device reduces the total cost of the device Through the understanding of the relationship between the carbon's degree of graphitization, crystallite surface and intercalation capacity, greatly improved energy storage is achieved
  • Figure (2) clearly shows the relationship of anion discharge capacity is opposite that of lithium as described by Matsumura, et al patent Accordingly, the anion preferentially stores/intercalates in the d002 spacing of the graphite, versus the surfaces or edges of the crystal structure of the carbon fiber Therefore, capacity is linked more closely to La than it is to Lc
  • Carbon fibers most preferred for anion intercalation/deintercalation electrodes have a crystallite surface calculated by 1/((Lc/d002)+1 ) of less than or equal to 0 025
  • the present invention provides a method for the use of continuous carbon fiber, not formed electrodes with binders as seen in much of the prior art (such as the reference by Steel, J A and Dahn, J R )
  • the present invention also provides for the use of a non-aqueous electrolyte, unlike some of the prior art references such as the reference by Noel, M and Santhanam, R
  • all tests performed on the fibers of the present invention were done in a dual graphite cell where the anode and cathode were both carbon fibers unlike the majority of the prior art (such as the reference by Santhanam, R and Noel, M )
  • a noble metal is only used occasionally as a reference electrode, but not as a counter or working electrode in the present invention Through extensive testing, it has been proven that the results of individual half-cells do not predict the final result of a completed dual graphite cell All components in the dual graphite technology depend on the other components, including the cation intercalating carbon fiber, the anion intercalating carbon fiber
  • the present invention is applicable to a wide variety of conductive materials
  • the present invention is applicable to various forms and grades of carbon and graphite particularly graphite fibers, formed from coal tar or petroleum pitches which are heat treated to graphitize to some degree the carbonaceous matter
  • the present application is applicable to the various polymers which on heating to above about 800C lose their non-carbon or substantially lose their non-carbon elements yielding a graphite like material (a material having substantial polyaromatic configurations or conjugated double bond structures) which results in the structure becoming conductive and are in part at least graphitic in form
  • Carbon/graphite fibers and their various forms, have the least amount of resistance in the axial direction, or along the length of the fiber Electrical and thermal energy is carried more efficiently along the length of a fiber than it is between fibers that are only in direct physical contact with each other, even when these fibers are held under pressure or with binders Binders themselves, though often called conductive, are not as conductive as the fiber itself Fibers that have only surface contacts with each other, have a large increased resistance between them due to these factors For these reasons, it is preferential to utilize all fibers in a manner that takes advantage of the low resistance axial direction For this reason, continuous fibers are often preferential to any form of carbon powder, chopped fibers, felt type mats, mesocarbon microbeads, etc
  • Continuous fibers of various forms are often preferred. For example, a woven cloth contains continuous fibers that run in two directions that are perpendicular to each other. This means that the woven cloth has fiber ends exposed on four sides.
  • the woven cloth then requires at least two edges of collection to utilize all carbon/graphite materials in the cloth, and thus takes more space and weight for current collection than for instance a unidirectional cloth, but less than is required for a graphite powder which would have one entire side of the material coated as a collector and would require a binder.
  • Unidirectional cloths, or braids such as biaxial or triaxial, contain continuous fibers that run in essentially one direction. The fibers start and then end with only two edges of exposed fiber ends; these then require only one edge of collection.
  • a carbon/graphite foam, or mat of thermally bonded fibers requires only one point of collection to attach all carbon/graphite together, since the material is fused together creating essentially one continuous fiber.
  • Figure (3) depicts these various carbon forms schematically.
  • the present invention includes the method and use of a unidirectional carbon fiber material.
  • U.S. Patent 5,677,084 refers to the use of a sheet of unidirectionally arranged carbon fibers; however, this prior art reference requires the fibers to be placed on a metal foil sheet, or the fibers are pasted and coated with a resin, that is in contact with the entire fiber surface.
  • (3)(b) shows carbon fibers laying in a parallel arrangement.
  • This fabric can be held in place by using a cross-stitch, or outer stitch, or with a web mat.
  • the present invention reduces weight, maintains cloth shape and improves handling of these unidirectional carbon fibers.
  • the unidirectional carbon fibers may be sprayed or covered with either polypropylene, polyethylene, or
  • the melting provides a stabilized fabric by melting the webbing/mat onto the carbon fiber
  • the mat can also be woven, but due to cost is more effectively a random or nonwoven
  • the mat can be applied directly to the fibers as they are oriented off a spool and then the fiber and polymer and/or glass mat can be run through a hot roller or other heat source such as IR lamps Several other processing options also exist with the same end product formed The end result is a stable and easily handled cloth
  • the unidirectional carbon fiber cloths can be of any size or shape, as determined by the end use
  • the material can be used as a battery electrode and separator pair where two sandwiches are placed adjacent to one another where the carbon acts as electrodes and the polymer as a separator
  • a thinner mat can be applied to the carbon and an additional layer of separator material is placed between the carbon/polymer sandwiches
  • the invention presented specifies the various types, and forms, of carbonaceous materials that are optimal for the use in dual graphite cells, which are incorporated to form dual graphite batteries
  • the dual graphite energy storage device is different from all other batteries
  • the dual graphite cell functions strictly on the intercalation and deintercalation of anions and cations, where no electrochemical reactions are required for energy storage and use
  • the carbonaceous materials used in dual graphite cells, and/or batteries, have requirements specific to this technology Improved anion intercalation and deintercalation capacity is seen as the degree of graphitization of the carbon fiber increases Exact electrode capacities differ depending upon the supporting electrolyte used, and depending upon the cation intercalation/deintercalation fiber used
  • the carbon fiber electrodes can be used in a dual graphite cell or battery, however those requiring the least amount of current collector are preferable
  • the dual graphite cell or battery obtains increasing levels of energy density as the continuous carbon fiber to current collector area ratio increases This means that the order of preferred materials are a carbon mat (in which the fibers are thermally fused to each other) and a carbon foam, a multiplicity of conductive fibers formed into a cloth form (such as a woven fabric, unidirectional mat, biaxial braid, tnaxial braid), a multiplicity of conductive fibers, and a single conductive fiber
  • a dual graphite cell was built through the following steps Unidirectional carbon cloth, of the design previously described, was cut to the desired size Current collectors were placed upon one edge of each electrode A thin layer of a typical battery separator was placed between the two electrodes The electrodes were placed in an air and watertight package The package void space was filled with a typical battery electrolyte Upon charge and discharge the dual graphite cell repeatably achieved 180mAh/g of both anion and cation capacity
  • graphite foam was used from various sources to make electrodes for cation intercalation and for anion intercalation in a dual graphite battery
  • Electrically conductive carbon ink was used to join the foam to a metal strip, and the metal was then coated to protect it from corrosion in the electrolyte
  • the foam materials for the two electrodes were in a one to one weight ratio
  • a thin layer of a typical battery separator was placed between the two electrodes
  • the electrodes were placed in an airtight and watertight package
  • the package void space was filled with a typical battery electrolyte

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Inorganic Fibers (AREA)
  • Woven Fabrics (AREA)
  • Arc Welding In General (AREA)
  • Inert Electrodes (AREA)

Abstract

La présente invention concerne un matériau de carbone destiné à une batterie au graphite double. Ce matériau de carbone comprend une matériau carboné présentant un module de Young supérieur à 75MSI. Cette invention concerne également un matériau de carbone conducteur utilisé dans un système de stockage d'énergie, ce matériau de carbone comprenant un matériau carboné choisi dans le groupe constitué essentiellement par une fibre conductrice unique, une multitude de fibres conductrices, des fibres conductrices formant une toile, une mousse de carbone et un mat de carbone dans lequel les fibres sont fusionnées par voie thermique. L'invention se rapporte en outre à un matériau ou à une fibre de carbone présentant une surface cristallitique calculée par 1/[(Lc/d002)+1] inférieure ou égale à 0,025 en vue d'une intercalation anionique, ainsi qu'à un procédé de fabrication d'une toile unidirectionnelle stabilisée par fixation d'une matière tissée à ce matériau carboné.
EP01908719A 2000-01-26 2001-01-26 Fibres de carbone pour batteries au graphite doubles Withdrawn EP1171923A1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US17821700P 2000-01-26 2000-01-26
US17824100P 2000-01-26 2000-01-26
US17817700P 2000-01-26 2000-01-26
US178241P 2000-01-26
US178217P 2000-01-26
US178177P 2000-01-26
PCT/US2001/002778 WO2001056100A1 (fr) 2000-01-26 2001-01-26 Fibres de carbone pour batteries au graphite doubles

Publications (1)

Publication Number Publication Date
EP1171923A1 true EP1171923A1 (fr) 2002-01-16

Family

ID=27390937

Family Applications (3)

Application Number Title Priority Date Filing Date
EP01903331A Withdrawn EP1183746A1 (fr) 2000-01-26 2001-01-26 Electrolytes pour systeme de stockage d'energie a graphite double
EP01903357A Withdrawn EP1180067A4 (fr) 2000-01-26 2001-01-26 Liaison thermique et electrique de faible resistance et son procede de fabrication
EP01908719A Withdrawn EP1171923A1 (fr) 2000-01-26 2001-01-26 Fibres de carbone pour batteries au graphite doubles

Family Applications Before (2)

Application Number Title Priority Date Filing Date
EP01903331A Withdrawn EP1183746A1 (fr) 2000-01-26 2001-01-26 Electrolytes pour systeme de stockage d'energie a graphite double
EP01903357A Withdrawn EP1180067A4 (fr) 2000-01-26 2001-01-26 Liaison thermique et electrique de faible resistance et son procede de fabrication

Country Status (5)

Country Link
EP (3) EP1183746A1 (fr)
JP (3) JP2003520687A (fr)
AU (3) AU2001231185A1 (fr)
CA (3) CA2365631A1 (fr)
WO (3) WO2001054856A1 (fr)

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US20090233175A1 (en) * 2005-03-31 2009-09-17 Kelley Kurtis C Current Carrier for an Energy Storage Device
GB2469449B (en) * 2009-04-14 2014-06-04 Energy Control Ltd Connecting structure for exteriorly connecting battery cells
DE102011054122A1 (de) * 2011-09-30 2013-04-04 Westfälische Wilhelms Universität Münster Elektrochemische Zelle
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US9509017B2 (en) * 2014-07-22 2016-11-29 John E. Stauffer Lithium storage battery
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Also Published As

Publication number Publication date
WO2001054856A1 (fr) 2001-08-02
AU2001231161A1 (en) 2001-08-07
JP2003521101A (ja) 2003-07-08
CA2368680A1 (fr) 2001-08-02
WO2001056100A1 (fr) 2001-08-02
CA2365631A1 (fr) 2001-08-02
EP1180067A4 (fr) 2004-03-31
AU2001236560A1 (en) 2001-08-07
JP2003520687A (ja) 2003-07-08
JP2003521102A (ja) 2003-07-08
WO2001056101A1 (fr) 2001-08-02
EP1183746A1 (fr) 2002-03-06
EP1180067A1 (fr) 2002-02-20
CA2365630A1 (fr) 2001-08-02
AU2001231185A1 (en) 2001-08-07

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