WO2007098478A2 - Électrochimie de sous-fluorures de carbone - Google Patents

Électrochimie de sous-fluorures de carbone Download PDF

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WO2007098478A2
WO2007098478A2 PCT/US2007/062518 US2007062518W WO2007098478A2 WO 2007098478 A2 WO2007098478 A2 WO 2007098478A2 US 2007062518 W US2007062518 W US 2007062518W WO 2007098478 A2 WO2007098478 A2 WO 2007098478A2
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subfluorinated
carbon
fluorine
coke
carbonaceous material
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PCT/US2007/062518
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English (en)
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WO2007098478A3 (fr
WO2007098478A9 (fr
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Rachid Yazami
Andre Hamwi
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California Institute Of Technology
Centre National De La Recherche Scientifique (C.N.R.S.)
Université Blaise Pascal
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Priority claimed from US11/422,564 external-priority patent/US7563542B2/en
Priority claimed from PCT/US2007/062243 external-priority patent/WO2007098369A2/fr
Priority claimed from US11/675,308 external-priority patent/US20070218364A1/en
Application filed by California Institute Of Technology, Centre National De La Recherche Scientifique (C.N.R.S.), Université Blaise Pascal filed Critical California Institute Of Technology
Priority to EP07757289A priority Critical patent/EP1999812A2/fr
Priority to JP2008555538A priority patent/JP2009527441A/ja
Priority to CN2007800060814A priority patent/CN101390234B/zh
Publication of WO2007098478A2 publication Critical patent/WO2007098478A2/fr
Publication of WO2007098478A3 publication Critical patent/WO2007098478A3/fr
Publication of WO2007098478A9 publication Critical patent/WO2007098478A9/fr

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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
    • C01B32/10—Carbon fluorides, e.g. [CF]nor [C2F]n
    • 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
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/22—Intercalation
    • 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
    • H01M4/5835—Comprising fluorine or fluoride salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • 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

Definitions

  • This invention is in the field of fluorinated carbon materials, in particular subfluorinated graphite and coke particles.
  • Fluorinated carbons are used commercially as a positive electrode material in primary lithium batteries. Fluorination of graphite allows intercalation of fluorine between the carbon layers.
  • Li/CF X battery systems are known to be capable of delivery of up to 700 Wh/kg, 1000 Wh/I, at room temperature, and at a rate of C/100 (i.e., a battery current of a 1/100 th that of the capacity of the battery per hour). (See, e.g., Bruce, G. Development of a CFx D Cell for Man Portable Applications, in Joint Service Power Expo. 2005; and Gabano, J. P., ed. Lithium Batteries, by M. Fukuda & T. lijima.
  • Cathodes in these systems typically have carbon - fluoride stoichiometries typically ranging from CFi.o ⁇ to CF 1 . 1 .
  • This cathode material is known to be discharge rate limited, and currents lower than C/50 (battery current 1/50 th that of the capacity of the battery divided by 1 hour) are often necessary to avoid cell polarization and large capacity loss.
  • High electronic resistivity up to 10 15 Ohm.cm of CF x is a potential cause of the observed discharge rate limitations, as there is a strong correlation between cathode thickness and performance; thicker cathodes tend to be more rate-limited. (See, e.g., V.N. Mittkin, J. Structural Chemistry, 2003, Vol. 44, 82-115, translated from Zhurnal Structunoi Khimii, 2003, Vol. 44, 99-138).
  • fluorinated carbons include use as solid lubricants or as reservoirs for very active molecular oxidizers such as BrF 3 and CIF 3 .
  • Poly(dicarbon monofluoride) is obtained at ⁇ 350 0 C and has a characteristic structure, where two adjacent fluorine layers are separated by two carbon layers bonded by strongly covalent C-C bonding along the c-axis of the hexagonal lattice (stage 2).
  • poly(carbon monofluoride) which is achieved at ⁇ 600 °C has a structure with only one carbon layer between two adjacent fluorine layers (stage 1).
  • Graphite fluorides obtained between 350 and 600 0 C have an intermediary composition between (CaF) n and (CF) n and consist of a mixture of these two phases (Kita, 1979, ibid.).
  • the stage s denotes the number of layers of carbon separating two successive layers of fluorine.
  • a compound of stage 1 has a sequence of stacking of the layers as FCF/FCF . . .
  • a compound of stage 2 has the sequence FCCF/FCCF . . . .
  • Both poly(dicarbon monofluoride) and poly(carbon monofluoride) are known to have relatively poor electrical conductivity.
  • U.S. Patent 3, 536,532 to Watanabe et al. describes a primary cell including a positive electrode having as the principal active material a crystalline fluorinated carbon represented by the formula (CF x ) n . where x is not smaller than 0.5 but not larger than 1. As described, the carbon is fluorinated by heating the reactor to the desired temperature then introducing fluorine.
  • U.S. Patent 3,700,502 to Watanabe et al. describes a battery including a positive electrode having as its active material an amorphous or partially amorphous solid fluoridated carbon represented by the Formula (CFx) n , wherein x is in the range of from greater than 0 to 1.
  • U.S. Patent 3, 536,532 to Watanabe et al. describes a primary cell including a positive electrode having as the principal active material a crystalline fluorinated carbon represented by the formula (CF x ) n . where x is not smaller than 0.5 but
  • Patent 4,247,608 to Watanabe et al. describes an electrolytic cell including a positive electrode having as the main active material a poly-dicarbon monofluoride represented by the formula (C 2 F) n wherein n is an integer.
  • Lam and Yazami (Lam, P. et al., 2006, J. Power Sources, 153, 354-359) present results for sub-fluorinated graphite fluorides (CF x ) n where 0.33 ⁇ x ⁇ 0.63.
  • Carbon-fluorine intercalation compounds have been also obtained by incorporating other compounds capable of acting as a fluorination catalyst, such as HF or other fluorides, into the gas mixture. These methods can allow fluorination at lower temperatures. These methods have also allowed intercalation compounds other than (C 2 F) n and (CF) n to be prepared (N. Watanabe et al., “Graphite Fluorides", Elsevier, Amsterdam, 1988, pp 240- 246).
  • intercalation compounds prepared in the presence of HF or of a metal fluoride have an ionic character when the fluorine content is very low (F/CO.1), or an iono-covalent character for higher fluorine contents (0.2 ⁇ F/C ⁇ 0.5).
  • the bonding energy measured by Electron Spectroscopy for Chemical Analysis (ESCA) gives a value less than 687 eV for the most important peak of the Fi s line and a value less than 285 eV for that of the Ci s line (T. Nakajima, Fluorine-carbon and Fluoride-carbon, Chemistry, Physics and Applications, Marcel Dekker 1995 p.13).
  • the invention provides subfluorinated graphite and coke materials which can provide enhanced cathode performance at high discharge rates compared to conventional CFi positive electrode active materials. These fluorinated materials are suitable for use in electrochemical devices such as primary batteries and secondary batteries. In particular, use of subfluorinated graphite and coke in lithium batteries can provide good battery performance at high discharge rates.
  • the subfluorinated carbonaceous materials of the invention are multicomponent materials having a fluorinated carbonaceous component and an unfluorinated carbonaceous component and/or a "lightly fluorinated" carbonaceous component in which fluorine is not strongly bound to carbon.
  • an unfluorinated and/or a "lightly fluorinated" carbonaceous component can provide higher electrical conductivity than would be obtained for a material consisting solely of the fluorinated phases poly(dicarbon monofluoride), poly(carbon monofluoride) and combinations thereof.
  • the subfluorinated graphite materials produced by the methods of the invention retain a greater amount of unfluorinated carbon, "lightly fluorinated” carbon, or a combinations thereof than materials of the same average F/C ratio produced with other types of fluorination processes known to the art.
  • the methods of the invention allow production of subfluorinated graphite materials having a fluorine to carbon ratio greater than 0.63 and less than or equal to 0.95.
  • the invention provides a method for making a subfluorinated carbonaceous material, the method comprising the steps of: a. providing a carbonaceous material selected from graphite particles or coke particles; b. exposing the carbonaceous material to a flowing gaseous source of elemental fluorine; c. heating the carbonacous material to a selected reaction temperature, the selected temperature being between 330 0 C and 600 0 C for graphite particles and 300 0 C and 500 0 C for coke particles; d. maintaining the carbonaceous material at the selected temperature for sufficient time to obtain a subfluorinated carbonaceous material.
  • the methods of the invention are capable of producing subfluorinated graphite materials having the average chemical composition CF x wherein 0.33 ⁇ x ⁇ 0.95 and subfluorinated coke materials having the average chemical composition CF x wherein 0.18 ⁇ x ⁇ 0.95.
  • the subfluorinated material has an average chemical composition CFx in which 0.63 ⁇ x ⁇ 0.95, 066 ⁇ x ⁇ 0.95, 0.7 ⁇ x ⁇ 0.95; or 0.7 ⁇ x ⁇ 0.9.
  • the amount of unfluorinated and "lightly fluorinated" carbon in the subfluorinated material is between 5% and 40%, between 5% and 37%, between 5% and 25%, between 10% and 20%, or about 15%.
  • the invention provides a subfluorinated carbonaceous material made by the process of: a. providing a carbonaceous material selected from graphite particles and coke particles; b. exposing the carbonaceous material to a flowing gaseous source of elemental fluorine; c. heating the carbonaceous material to a selected reaction temperature, the selected temperature being between 330 0 C and 600 0 C for graphite particles and 300°C and 500°C for coke particles; and d. maintaining the carbon material at the selected temperature for sufficient time to obtain a subfluorinated carbonaceous material having an average chemical composition CFx where 0.63 ⁇ x ⁇ 0.95.
  • the invention also provides subfluorinated graphite materials having an average chemical composition CF x in which 0.63 ⁇ x ⁇ 0.95, wherein 13 C nuclear magnetic resonance spectroscopy analysis of the subfluorinated graphite provides a spectrum comprising at least one chemical shift peak centered between approximately 100 and 150 ppm relative to TetraMethylSilane (TMS) and another chemical shift peak centered at approximately 84-88 ppm relative to TMS.
  • TMS TetraMethylSilane
  • the invention also provides a subfluorinated coke material prepared by direct fluoridation of coke having a coherence length L c between 5nm and 20 nm, the subfluorinated coke material having an average chemical composition CF x in which 0.63 ⁇ x ⁇ 0.95.
  • 13 C nuclear magnetic resonance spectroscopy analysis of the subfluorinated coke provides a spectrum comprising at least one chemical shift peak centered between approximately 100 and 150 ppm relative to TetraMethylSilane (TMS) and another chemical shift peak centered at approximately 84-88 ppm relative to TMS.
  • Figure 1 shows X-ray diffraction spectra for subfluorinated graphite materials with a range of F/C ratios.
  • Figure 2 X-ray diffraction spectrum for a subfluorinated graphite material with an F/C ratio of 0.9. The labels above the peaks are the calculated d-spacings.
  • Figure 3 13 C Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR) spectra for several subfluorinated graphite materials. (10 kHz)
  • Figure 4 13 C NMR spectrum for a subfluorinated graphite material having an F/C ratio of 0.77.
  • Figure 5 Plot of %C grap hitic and %C sp3 versus the F/C ratio for several subfluorinated graphites synthesized at 390 "C.
  • Figure 6 Ragone plot for several subfluorinated graphites versus CF 1 .
  • Figure 9 Discharge curve for subfluorinated graphite CF 0 . 744 -
  • Figure 10 Discharge curve for subfluorinated graphite CF 0 . 647 -
  • Figure 11 X-ray diffraction spectrum for a subfluorinated coke material with an F/C ratio of 0.36.
  • Figure 14 X-ray diffraction spectrum for a subfluorinated coke material with an F/C ratio of 0.95.
  • Figure 15 13 C Magic Angle Spinning(MAS) Nuclear Magnetic Resonance (NMR) spectra for several subfluorinated coke materials. (10 kHz)
  • Figure 16 13 C NMR spectrum for a subfluorinated coke material having an F/C ratio of 0.73.
  • Figure 17 Ragone plot for several subfluorinated coke materials versus CF 1 .
  • Figure 18 Discharge curves for subfluorinated coke material CF 0 . 97 .
  • Figure 19 Discharge curves for subfluorinated coke material CF 0 . 87 .
  • Figure 20 Discharge curves for subfluorinated coke material CF 0 . 63 -
  • the invention provides subfluorinated carbonaceous materials obtained through direct fluorination of graphite or coke particles.
  • Subfluorinated carbonaceous materials obtained through fluorination of graphite particles may also be referred to as subfluorinated graphites or subfluorinated graphite materials herein.
  • subfluorinated carbonaceous materials obtained through fluorination of coke particles may also be referred to as subfluorinated cokes or subfluorinated coke materials herein.
  • Coke is a carbonaceous material which is typically formed from petroleum or coal pitch.
  • the structure of coke materials depends on the heat treatment temperature of the material. In the temperature range above about 2100 0 C, coke converts to crystalline graphite. At lower temperatures, between about 1500 0 C and about 2100 0 C, the carbon layers are disordered, with turbostratic stacking defects. At even lower temperatures, between about 700 0 C and 1500 0 C, the structure can be described as having bent columns.
  • the structure may be characterized by the coherence length L c , which relates to the crystallite dimension in the c- direction and can be determined from X-ray diffraction analysis.
  • coke suitable for use with the present invention has a coherence length U along the c-axis perpendicular to the carbon layers greater than about 5 nm and less than about 20 nm.
  • substituted carbonaceous material refers to a multicomponent carbonaceous material having a fluorinated carbonaceous component in which at least some of the carbon is strongly bound to fluorine and an unfluorinated carbonaceous component and/or a "lightly fluorinated” carbonaceous component in which fluorine is not strongly bound to carbon.
  • Multiphase subfluorinated carbonaceous materials may comprise a mixture of carbonaceous phases including, an unfluorinated carbonaceous phase (e.g., graphite or coke), a "lightly fluorinated” phase and one or more fluorinated phases (e.g., poly(carbon monoflouride (CFi); poly(dicarbon monofluoride) etc.).
  • Subfluorinated carbonaceous materials include carbonaceous materials exposed to a fluorine source under conditions resulting in incomplete or partial fluorination of a carbonaceous starting material.
  • Partially fluorinated carbon materials include materials in which primarily the exterior portion has reacted with fluorine while the interior region remains largely unreacted.
  • fluorination of a material involves introduction of fluorine into the material.
  • fluorination will typically involve formation of bonds between carbon and fluorine.
  • fluorine is capable of forming both ionic and covalent bonds with carbon.
  • C-F bonds have also been classified as intermediate in strength between ionic and covalent bonds (e.g. partially ionic, semi-ionic, semi-covalent).
  • the fluorination method can influence the type of bonding present in the fluorination product.
  • the fluorinated carbon materials are produced by direct fluorination.
  • direct fluorination at least some of the C-F bonds formed tend to be of higher energy and have a stronger, more covalent character than the C-F bonds obtained through low temperature fluorine intercalation.
  • Fluorine-graphite intercalation compounds are expected to have carbon-fluorine bonding varying between the ionic and the semi- covalent depending on the fluorine content (Matsuo, Y. et al, 1995 Z. Anorg. AIIg. Chemie, 621, 1943-1950). For example, Matsuo et al.
  • At least some of the carbon in the fluorination product is strongly bound to fluorine (covalently bound or nearly covalently bound to fluorine).
  • a carbon-fluorine bond in the fluorination product is classified as nearly covalent if the bond has an energy greater than the energy of "semi-ionic" or “semi-covalent” carbon-fluorine bonds in graphite intercalation compounds of fluorine obtained through low temperature fluorination of graphite, but less than the typical energy of covalent carbon- fluorine bonds in poly(dicarbon monofluoride) (C 2 F) n or poly(carbon monofluoride) (CF) n .
  • the subfluorinated carbonaceous material comprises a "lightly fluorinated" carbonaceous component in which fluorine is not strongly bound to carbon.
  • the F-C bond energy in such a carbonaceous component is less than that of a covalent or nearly covalent F- C bond.
  • the nature of the C-F bonding in the fluorination product may be determined by suitable analysis techniques.
  • Such techniques include, but are not limited to, Fourier Transform Infrared Spectroscopy (FT-IR), Nuclear Magnetic Resonance Spectroscopy (NMR), X-Ray Photoelectron Spectroscopy (XPS) or Electron Spectroscopy for Chemical Analysis (ESCA).
  • FT-IR Fourier Transform Infrared Spectroscopy
  • NMR Nuclear Magnetic Resonance Spectroscopy
  • XPS X-Ray Photoelectron Spectroscopy
  • ESA Electron Spectroscopy for Chemical Analysis
  • the extent of covalency in the C-F bonds can be assessed by comparison of the analysis results for the fluorination product to those obtained for a "standard” commonly accepted to have covalent C-F bonds. A match (within experimental error) between the analysis results for the fluorination product and those of the "standard” may be taken to indicate covalent bonding.
  • solid state 19 F-NMR spectra having a chemical shift peak centered at about -190 ppm /CFCI 3 indicate fluorine atoms covalently bonded to carbon atoms.
  • solid state 13 C- NMR spectra having a resonance present at a chemical shift of 84-88 ppm/TMS indicate carbon atoms covalently bound to fluorine atoms (Giraudet J.; Dubois M.; Guerin K.; Hamwi A.; Masin F.; J. Phys. Chem. Solids 2006, 67(5-6), 1100).
  • FT-IR Fourier Transform Infrared Spectroscopy
  • 13 C-NMR analysis of the subfluorinated materials of the invention gives a spectrum which comprises a chemical shift peak centered at approximately 84-88 ppm relative to TMS, indicating carbon atoms strongly bound to fluorine atoms.
  • Solid state 13 C-NMR spectra of fluorinated graphite material having a resonance present at a chemical shift of about 136 ppm/TMS has been interpreted as indicating "graphitic" sp 2 -type carbon atoms which are either non-fluorinated or in a low interaction with fluorine (Giraudet, 2006 ibid.).
  • solid state 13 C-NMR spectra of graphite material can display a resonance present at a chemical shift of about 119 ppm/TMS (Giraudet, 2006 ibid.).
  • 13 C nuclear magnetic resonance spectroscopy analysis of the subfluorinated carbonaceous materials of the invention provides a spectrum comprising at least one chemical shift peak centered between approximately 120 and 140 ppm relative to TMS 7 indicating "graphitic" carbon either not bonded or only weakly bonded to fluorine.
  • an XRD spectrum of the subfluorinated graphite or coke comprises a substantial peak at 2 ⁇ approximately in the range 25.5-26.4 degrees, using Cu K 0 radiation, corresponding to the graphite or coke (002) peaks.
  • an XRD spectrum of the subfluorinated graphite does not comprise a substantial peak at 2 ⁇ approximately in the range 26.3-26.4 degrees, using Cu K 0 radiation.
  • the relative amount of graphitic carbon atoms can be estimated through comparison of the areas of chemical shift peaks in a 13 C-NMR spectra.
  • the sum of the area of the peaks corresponding to nonfluorinated and “lightly” fluorinated carbon is divided by the sum of these peaks with the peak corresponding to carbon in strong interaction with fluorine and (if present) the peak corresponding to a strong carbon-carbon interaction. Additional peaks may be included in the denominator, as explained in Example 5, which relates to subfluorinated coke materials. If any peak is not clearly seen in the spectrum, it not included in the sum.
  • the average ratio of fluorine to carbon may be used as a measure of the extent of fluorination. This average ratio may be determined through weight uptake measurements or through quantitative NMR measurements. When fluorine is not uniformly distributed through the wall thickness of the carbon material, this average ratio may differ from surface fluorine to carbon ratios as may be obtained through x-ray photoelectron spectroscopy (XPS) or ESCA.
  • XPS x-ray photoelectron spectroscopy
  • ESCA x-ray photoelectron spectroscopy
  • fluorination of graphite and heat treated coke at relatively low temperatures is believed to result primarily in fluorination of the surface of the carbon material. The remainder of the carbon material remains unfluorinated. This surface fluorination may include formation of groups such as CF 2 , and CF 3 .
  • the fluorinated graphite product has some crystallographic similarities to a mixture of graphite fluorides (C 2 F) n and (CF) n .
  • the average interlayer spacing may be intermediate between that of graphite poly(dicarbon mo ⁇ ofluoride) and that of graphite pofy(carbon monofluoride).
  • the fluorinated coke product has some crystallographic similarities to (CF) n .
  • the subfluorinated carbonaceous material comprises a plurality of nanostructured particles; wherein each of the nanostructured particles comprise a plurality of fluorinated domains and a plurality of unfluorinated or "lightly" fluorinated domains.
  • a "domain” is a structural component of a material having a characteristic composition (e.g., unfluorinated or fluorinated), phase (e.g., amorphous, crystalline, C 2 F 1 CF 1 , graphite, coke.), and/or morphology.
  • Useful subfluorinated carbonaceous materials for positive electrode active materials comprise a plurality of different domains.
  • Individual fluorinated, "lightly fluorinated” and unfluorinated domains preferably for some applications have at least one physical dimension (e.g., lengths, depths, cross sectional dimensions etc.) less than about 50 nanometers, and more preferably for some applications at least one physical dimension less than about 10 nanometers.
  • Positive electrode active materials particularly useful for electrochemical cells providing high performance at low temperatures include nanostructured particles having fluorinated domains and unfluorinated or "lightly" fluorinated domains that are distributed throughout each nanostructured particle of the active material, and in some embodiments substantially uniformly distributed throughout each nanostructured particle of the active material.
  • fluorinated domains of particles of the positive electrode active material comprise a subfluorinated carbonaceous material having an average stoichiometry CFy 1 wherein y is the average atomic ratio of fluorine atoms to carbon atoms and is selected from the range of about 0.8 to about 1.0, and the unfluorinated domains of the particles of the positive electrode active material comprise a unfluorinated carbonaceous phase, such as graphite or coke.
  • nanostructured refers materials and/or structures have a plurality of discrete structural domains with at least one physical dimension (e.g., height, width, length, cross sectional dimension) that is less than about 1 micron.
  • structural domains refer to features, components or portions of a material or structure having a characteristic composition, morphology and/or phase.
  • Nanostructured materials useful as positive electrode active materials, particularly under high discharge rates and/or at low temperatures include nanostructured composite particles having a plurality of fluorinated carbon domains and unfluorinated or "lightly fluorinated” carbon domains.
  • nanostructured materials of the present invention comprise a plurality of structural domains having different compositions, morphologies and/or phase intermixed on a very fine scale (e.g., at least smaller than 10's of nanometers).
  • nanostructured subfluorinated carbonaceous particles as positive electrode active materials provides a number of benefits in electrochemical cells of the present invention.
  • nanoscale intermixing of fluorinated and unfluorinated or "lightly" fluorinated domains in these particles results in high interfacial surface areas between the fluorinated and unfluorinated domains. This attribute provides good electronic and interface properties between these domains facilitating electron transfer, particularly at low temperatures.
  • the presence of an appreciable unfluorinated or "lightly” fluorinated component in these particles enhances net electrode conductivity by providing nanoscale electrically conducting pathways in the electrode active material.
  • nanoscale fluorinated domains in these materials provides an appreciable density of fluorinated domains having high fluorine ion loading exposed to the electrolyte, thereby resulting in a high interfacial surface area of fluorinated structural domains exposed to the electrolyte further enhancing the kinetics at the positive electrode.
  • Subfluorinated carbonaceous particles comprising positive electrode active materials in the present invention may have a wide range of physical dimensions, for example cross sectional dimensions ranging from about 100 nanometers to about 200 microns and lateral dimensions range from about 100 nanometers to about 500 microns.
  • carbonaceous particles useful in positive electrodes of the present electrochemical cells are porous.
  • aspect ratio (longitudinal physical dimensions (e.g., length )/(cross sectional physical dimension (e.g., diameter)
  • aspect ratios selected from the range of about 50 to about 1000.
  • carbonaceous particles useful in positive electrodes of the present electrochemical cells have a flake shapes and/or have a morphologies similar to unfluor
  • the fluorinated carbonaceous materials of the invention are prepared using a direct fluorination method, in which the graphite or coke particles are contacted with a gaseous source of elemental fluorine.
  • the fluorination conditions including mass of carbonaceous material, reaction temperature, reaction time, and fluorine flow rate) are selected to obtain the desired degree of fluorination of the carbon materials.
  • the graphite or coke powder is uniformly spread on a nickel boat and introduced into a reactor.
  • the reactor may be made of nickel, and have a horizontal setting.
  • the reactor may be vacuum degassed prior to starting flow of fluorine gas.
  • the reaction proceeds under fluorine dynamic flow (open reactor). (It is believed that if the reactor is closed (static reactor), the fluorination reaction becomes much slower.).
  • the reactor is then heated.
  • the reaction time is counted after the reactor reached the target temperature until the reactor heating is stopped.
  • excess (unreacted) fluorine may be evacuated under nitrogen flow until no trace of free fluorine is in the reactor.
  • the reactor is heated at the rate between 0.5 degrees Celsius / minute and 5 degrees Celsius/minute. In an embodiment, the reactor is heated at the rate of 1 degrees Celsius / minute.
  • the fluorination temperature for graphite particles may be between 330 0 C and 600 0 C, between 375 0 C and 550 0 C , or between 390° C and 490 0 C . Weight loss due to volatile carbon-fluorine compounds is expected to occur at about 550 0 C.
  • the fluorination temperature for coke particles may be between 300 0 C and 550 0 C, between 350 0 C and 450 0 C , or between 370° C and 425 0 C . Weight loss due to volatile carbon-fluorine compounds is expected to occur at about 450 0 C.
  • the time period is greater than 2 hours, between 2 and 40 hours, between 3 and 30 hours, between 4 and 20 hours, between 4 and 16 hours, between 4 and 12 hours, between 8 and 20 hours, between 8 and 16 hours, between 8 and 12 hours, or about 16 hours.
  • the fluorination is conducted at atmospheric pressure with a gas mixture essentially consisting of F 2 and inert gas.
  • the percentage of fluorine in the mixture may be between 5% and 100%, between 10% and 90%, between 20% and 80%, between 20% and 60%, between 20% and 50% or about 20%.
  • the fluorine flow rate is between 0.5 and 2.0 g/fluorine per hour
  • the average particle size of the carbonaceous material is 2-200 microns, 5-50 microns, or 5-20 microns.
  • the fluorination may be conducted at a pressure less than atmospheric pressure. In an embodiment, the fluorination may be conducted at pressures between 1 atm and 0.1 atm, or between 1 atm and 0.25 atm.
  • a suitable gaseous source of elemental fluorine will be known to one of ordinary skill in the art; an exemplary such source is a mixture F2 and a sufficiently inert gas.
  • Suitable inert gases include, but are not limited to nitrogen, and argon.
  • the subfluorinated carbonaceous material of the invention can be heat treated following fluorination.
  • Electrochemical cell refers to devices and/or device components that convert chemical energy into electrical energy or electrical energy into chemical energy. Electrochemical cells typically have two or more electrodes (e.g., positive and negative electrodes) wherein electrode reactions occurring at the electrode surfaces result in charge transfer processes. Electrochemical cells include, but are not limited to, primary batteries, secondary batteries, lithium batteries and lithium ion batteries. General cell and/or battery construction is known in the art, see e.g., U.S. Pat. Nos. 6,489,055, 4,052,539, 6,306,540, Seel and Dahn J. Electrochem. Soc. 147(3) 892-898 (2000).
  • Capacity is a characteristic of an electrochemical cell that refers to the total amount of electrical charge an electrochemical cell, such as a battery, is able to hold. Capacity is typically expressed in units of ampere- hours.
  • specific capacity refers to the capacity output of an electrochemical cell, such as a battery, per unit weight. Specific capacity is typically expressed in units of ampere-hours kg “1 . The theoretical specific capacity is referred to as Q t h-
  • discharge rate refers to the current at which an electrochemical cell is discharged.
  • Discharge current can be expressed in units of amperes.
  • discharge current can be expressed as 'C/n" rate, where n is the number of hours theoretically needed to fully discharge the cell. For example, under C/5 rate and 3C rate, the full discharge is expected to be reached in 5 hours and 20 minutes, respectively.
  • I x is the discharge current intensity in units of current per unit weight (e.g. mA/g).
  • Active material refers to the material in an electrode that takes part in electrochemical reactions which store and/or deliver energy in an electrochemical cell.
  • the present invention provides electrochemical cells having a positive electrode with a subfluorinated carbonaceous active material.
  • Room temperature refers to a temperature selected over the range of about 293 to 303 degrees Kelvin.
  • the subfluorinated carbonaceous materials are normally present in a composition that also includes a conductive diluent such as may be selected from, for example, acetylene black, carbon black, powdered graphite, cokes, carbon fibers, carbon nanotubes and metallic powders such as powdered nickel, aluminum, titanium, and stainless steel.
  • a conductive diluent such as may be selected from, for example, acetylene black, carbon black, powdered graphite, cokes, carbon fibers, carbon nanotubes and metallic powders such as powdered nickel, aluminum, titanium, and stainless steel.
  • the conductive diluent improves conductivity of the composition and is typically present in an amount representing about 1 wt.% to about 10 wt.% of the composition, preferably about 3 wt.% to about 8 wt.% of the composition.
  • the composition containing the subfluorinated carbonaceous materials and the conductive diluent also, typically, contains a polymeric binder, with preferred polymeric binders being at least partially fluorinated.
  • binders thus include, without limitation, poly(ethylene oxide) (PEO), poly(vinylidene fluoride) (PVDF), a poly(acrylonitrile) (PAN), poly(tetrafluoroethylene) (PTFE), and poly(ethylene-co-tetrafluoroethylene) (PETFE).
  • the binders if present, represent about 5 wt.% to about 15 wt.% of the composition, while the subfluorinated carbonaceous material represent about 70 wt.% to about 90 wt.% of the composition, preferably about 75wt.% to 85 wt.% of the composition.
  • the resulting subfluorinated carbonaceous material is then admixed with a conductive diluent and binder as described above, with the preferred weight ratios being about 70 wt/% to about 90 wt.%, more preferably about 75 wt.% to about 85 wt.% of subfluorinated carbonaceous material; about 1 wt.% to about 10 wt.%, preferably about 3 wt.% to about 8 wt.%, conductive diluent; and about 5 wt.% to about 15 wt.% binder.
  • the slurry formed upon admixture of the foregoing components is then deposited or otherwise provided on a conductive substrate to form the electrode.
  • a particularly preferred conductive substrate is aluminum, although a number of other conductive substrates can also be used, e.g., stainless steel, titanium, platinum, gold, and the like.
  • the subfluorinated particles are elongated, they may be at least partially aligned during the deposition process. For example, shear alignment may be used to align the subfluorinated particles.
  • a method for preparing an electrode for use in an electrochemical device comprising the following steps:
  • Preparing a subfluorinated carbonaceous material according to the methods of the invention Preparing a subfluorinated carbonaceous material according to the methods of the invention; mixing the subfluorinated material with a conductive diluent and a binder to form a slurry; and applying the slurry to a conductive substrate.
  • the invention provides an electrochemicaf device comprising a first electrode and a second electrode, and an ion transporting material disposed therebetween, wherein the first electrode comprises a subfluorinated carbonaceous material according to the present invention.
  • the aforementioned electrode serves as the cathode, with the anode providing a source of lithium ions, wherein the ion-transporting material is typically a microporous or nonwoven material saturated with a nonaqueous electrolyte.
  • the anode may comprise, for example, a foil or film of lithium or of a metallic alloy of lithium (LiAI, for example), or of carbon-lithium, with a foil of lithium metal preferred.
  • the ton-transporting material comprises a conventional "separator" material having low electrical resistance and exhibiting high strength, good chemical and physical stability, and overall uniform properties.
  • Preferred separators herein are microporous and nonwoven materials, e.g., nonwoven polyolefins such as nonwoven polyethylene and/or nonwoven polypropylene, and microporous polyolefin films such as microporous polyethylene.
  • An exemplary microporous polyethylene material is that obtained under the name Celgard ® (e.g., Celgard ® 2400, 2500, and 2502) from Hoechst Celanese.
  • the electrolyte is necessarily nonaqueous, as lithium is reactive in aqueous media.
  • Suitable nonaqueous electrolytes are composed of lithium salts dissolved in an aprotic organic solvent such as propylene carbonate (PC), ethylene carbonate (EC), ethyl methyl carbonate (EMC) 1 dimethyl ether (DME), and mixtures thereof. Mixtures of PC and DME are common, typically in a weight ratio of about 1:3 to about 2:1.
  • Suitable lithium salts for this purpose include, without limitation, LiBF 4 , LiPF 6 , LiCF 3 SO3, LiCIO 4 , LiAICU, and the like.
  • a change in voltage causes generation of lithium ions at the anode and migration of the ions through the electrolyte-soaked separator to the subfluorinated carbonaceous material of the cathode, "discharging" the battery.
  • the invention provides an electrochemical device wherein the device is a primary lithium battery in which the first electrode acts at the cathode, the second electrode acts at the anode and comprises a source of lithium ions, and the ion-transporting material physically separates the first and the second electrode and prevents direct electrical contact therebetween.
  • the subfluorinated carbonaceous material is utilized in a secondary battery, i.e., a rechargeable battery such as a rechargeable lithium battery.
  • a secondary battery i.e., a rechargeable battery such as a rechargeable lithium battery.
  • the cations e.g., lithium ions
  • the subfluorinated electrode where they are intercalated and de-intercalated by the subfluorinated material.
  • solid polymer electrolytes examples include chemically inert polyethers, e.g., poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), and other polyethers, wherein the polymeric material is impregnated or otherwise associated with a salt, e.g., a lithium salt such as those set forth in the preceding paragraph.
  • a salt e.g., a lithium salt such as those set forth in the preceding paragraph.
  • gelled polymer electrolytes examples include polyvinylene difluoride (PVDF) homo- or co-polymer impregnated or otherwise associated with a non-aqueous electrolyte such as those set forth in the preceding paragraph.
  • PVDF polyvinylene difluoride
  • the invention provides an electrochemical device, wherein the device is a secondary battery in which the second electrode comprises a source of ions of a metal selected from Groups 1, 2, and 3 of the Periodic Table of Elements and the ion-transporting material comprises a solid polymer electrolyte that permits transport of said metal cations and physically separates the first and second electrodes.
  • a rechargeable battery includes: a first electrode comprising a subfluorinated carbonaceous material, the electrode capable of receiving and releasing cations of a metal selected from Groups 1, 2, and 3 of the Periodic Table of the Elements; a second electrode comprising a source of the metal cations; and a solid or a gelled polymer electrolyte that permits transport of the metal cations and physically separates the first and second electrodes.
  • Exemplary discharge profiles of Li/subfluorinated graphite cells are shown in Figures 7-10 and exemplary profiles of Li/subfluorinated coke cells are shown in Figures 18-20. These cells exhibit a characteristic plateau corresponding to the formation of LiF according to Equation 1. The value of the plateau voltage depends upon the discharge rate.
  • the discharge profiles of these cells differ depending on the fluorine to carbon ratio of the subfluorinated material. In general, the higher F/C, the higher the discharge capacity, as indicated by Equation 2.
  • Subfluorinated carbonaceous materials can show reduced over- potential for low discharge times as compared to fully fluorinated materials. This is related to the decrease of electrical conductivity of the sample when the fluorinated parts progress i. e. the decrease of pristine carbon amount in the sample.
  • cells including Li and subfluorinated carbonaceous material can display improved performance as compared to commercial Li/CF cells at higher discharge rates (e.g. at or above 1C) and higher power densities.
  • discharge rates e.g. at or above 1C
  • power densities e.g. at or above 1C
  • Wh/kg energy density
  • the electrochemical cell may be "pre-discharged" before being put into actual use.
  • the pre-discharge step involves discharging from 1%-5% of the capacity of the cell.
  • Pre- discharge of the cell can eliminate the initial voltage delay before establishment of the voltage plateau which is seen in the characteristic discharge profile of a Li/subfluorinated carbonaceous material cells.
  • EXAMPLE 1 Synthesis of Subfluorinated Graphite [00092] Graphite ((10 to 30 grams, quantity, M, of Natural Graphite of Madagascar 7.5 ⁇ m or Artificial Graphite 15 - 20 ⁇ m distributed on a nickel plate, 0.2 g / cm 2 ) was placed into the nickel reactor (4 litre), and dried under vacuum at room temperature during 2 hours. Then, fluorine gas (99,90 % purity) was introduced up to 1 atmosphere and after, using open system reactor, fluorine was flowed with controlled rate (FL g / hour). Afterward, the temperature was regularly increased (1 0 C / min) to the final temperature T ( 0 C) and was maintained during H hours.
  • fluorine gas 99,90 % purity
  • FIG. 1 shows X-ray diffraction spectra for a subfluorinated graphite materials with range of F/C ratios.
  • the spectra show peaks characteristic of a fluorographite matrix at 20 between approximately 10 and 15 degrees and between approximately 40 and 45 degrees.
  • a peak at 2 ⁇ 26.3, which is the position characteristic of the (002) graphite peak, is clearly observed for CF0.34, CF 0 .4s and CF0.57.
  • Figure 2 shows an enlarged view of an X-ray diffraction spectrum for a subfluorinated graphite material with an F/C ratio of 0.9.
  • the spectrum shows peaks characteristic of a fluorographite matrix at 2 ⁇ of approximately 13 degrees (002) and approximately 41 degrees (100). Additional peaks are located at 2 ⁇ of approximately 28 degrees (004) and 75 degrees (110).
  • the labels above the peaks are the calculated d-spacings (e.g the label 6,628 corresponds to a spacing of 6.628 Angstroms).
  • the spacings (d) calculated are 6.628 Angstroms for (002), 3.258 Angstroms for (004), 2.201 Angstroms for (100) and 1.273 Angstroms for (110).
  • Figure 3 shows 13 C Magic Angle Spinning(MAS) Nuclear Magnetic Resonance (NMR) spectra for several subfluorinated graphite materials. (10 kHz). The subfluorinated graphite materials were synthesized at a reaction temperature of 390 0 C.
  • the dotted lines overlaid on the spectra indicate the characteristic positions of peaks for diamond-like sp 3 -hybridized carbon atoms (at 42-43 ppm/TMS) and carbon in strong interaction with fluorine (C-F) (at about 88 ppm/TMS), and the observed positions attributed to graphite-like sp 2 -hybridized carbon atoms (C G ) (at about 120 ppm/TMS) and carbon atoms in weak interaction with fluorine (C — F) (at about 140 ppm/TMS).
  • Figure 4 shows an 13 C NMR spectrum for a subfluorinated graphite material having an F/C ratio of 0.9.
  • the peak attributed to diamond-like sp 3 -hybridized carbon atoms has been labeled C and the peak attributed to carbon in strong interaction with fluorine (C-F) has been labeled B.
  • the combination of peaks A and A' is associated with the contribution of graphite-like sp 2 -hybrized carbon atoms and carbon atoms in weak interaction with fluorine (C — F).
  • Peak A is more closely associated with carbon atoms in weak interaction with fluorine while peak A' is more closely associated with graphite-like sp 2 -hybrized carbon atoms.
  • the data was normalized with a Lorentzian function and deconvoluted (Origin 7.5 software, OriginLab). The result is shown by the dashed lines in Figure 4.
  • the sum of the area of deconvoiuted peaks A and A' divided by the sum of the area of deconvoluted peaks A, A',, B and C is 19%. Similar area ratios for A and A', respectively, are 8% and 11%.
  • Table 1 shows data obtained for CF1 and subfluorinated graphites with F/C ratios of 0.65, 0.77, and 0.9.
  • Figure 5 is a plot of the percent of graphitic carbon and sp 3 type carbon versus F/C ratio derived from the spectra in Figure 3.
  • Example 3 Electrochemical Properties of Subfluorinated Graphite
  • the positive electrodes were composed of subfluorinated carbonaceous material, a conductive material and a binder. The positive electrode was then mounted in a two electrode cell where the electrolyte was composed of a imol.L '1 solution of LJBF 4 dissolved in propylene carbonate (PC) and dimethyl ether (DME). A microporous polyethylene or polypropylene film containing the electrolyte was sandwiched between the graphite fluoride electrode and a lithium metal foil.
  • PC propylene carbonate
  • DME dimethyl ether
  • Figure 6 shows a Ragone plot of energy density versus the square root of power density.
  • Subfluorinated graphites CF0. 9 0, CF0.77 and CF0.744 have significantly higher energy densities than CF for power densities greater than 625 W/kg.
  • Figures 7-10 show discharge profiles for subfluorinated graphites CF o.9, CF 0.77, CF 0.744, and CF 0.647, respectively.
  • the electrode thicknesses were approximately 80 microns, 40 microns, 40 microns and 120 microns, respectively.
  • Coke (quantity, M, is 2 grams distributed on nickel boat) was placed into the nickel reactor (1 litre), and dried under vacuum at room temperature during 2 hours. Then, fluorine gas (99,90 % purity) was introduced up to 1 atmosphere and after, using open system reactor, fluorine was flowed with controlled rate (FL g / hour). Afterward, the temperature was regularly increased (1 0 C / min) to the final temperature T ( 0 C) and was maintained during H hours. At the end of the reaction, the furnace was cooled to room temperature. Next, the excess of fluorine was evacuated under dry nitrogen flow during 1 hours. (Note: F/C molar ratios of the subfluorinated cokes were measured by the weight uptake method.)
  • Fluorine flow rate FL 2 g / hour
  • the spectrum shows peaks for fluorinated phases at 2 ⁇ equal to approximately 13 degrees, 41 degrees, 43.5 and 44.4 degrees, a peak for a coke phase at 2 ⁇ equal to approximately 25.8 degrees, and peaks for the silicon reference at 2 ⁇ equal to approximately 28.4 and 47.3 degrees.
  • the height of the peak associated with the coke phase decreases with increasing F/C, as expected.
  • FWHM is the full width at half maximum.
  • Figure 15 shows 13 C Magic Angle Spinning(MAS) Nuclear Magnetic Resonance (NMR) spectra for several subfluorinated coke materials. (10 kHz).
  • the dotted lines overlaid on the spectra indicate the characteristic positions of peaks for diamond-like sp 3 -hybridized carbon atoms (at 42-43 ppm/TMS) and carbon in strong interaction with fluorine (C-F) (at about 88 ppm/TMS), and the observed positions attributed to graphite-like sp 2 -hybridized carbon atoms (C G ) (at about 120 ppm/TMS) and carbon atoms in weak interaction with fluorine (C — F) (at about 140 ppm/TMS).
  • C G graphite-like sp 2 -hybridized carbon atoms
  • C G graphite-like sp 2 -hybridized carbon atoms
  • C G graphite-like sp 2 -h
  • Example 6 Electrochemical Properties of Subfluorinated Coke
  • the positive electrodes were composed of subfluorinated carbonaceous material, a conductive material and a binder. The positive electrode was then mounted in a two electrode cell where the electrolyte was composed of a imol.L "1 solution of LiBF 4 dissolved in propylene carbonate (PC) and dimethyl ether (DME). A microporous polyethylene or polypropylene film containing the electrolyte was sandwiched between the graphite fluoride electrode and a Fithiurn metal foil.
  • PC propylene carbonate
  • DME dimethyl ether
  • Figure 17 shows a Ragone plot of energy density versus the square root of power density.
  • Subfluorinated cokes CF 0 .64 and CF ⁇ 84 have significantly higher energy densities than CF for power densities greater than 900 W/kg.
  • Figures 18-20 show discharge profiles for subfluorinated coke material CF 0.97, CF 0 .87, and CF 0 .63, respectively.
  • Table 4 presents electrochemical data for subfluorinated Coke Materials.
  • ⁇ e> is the average discharge voltage under a fixed discharge rate
  • Q achieved discharge capacity (mAh/g)
  • E achieved energy density (Wh/kg).

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Abstract

L'invention concerne des matières carbonées sous-fluorées obtenues par fluoration directe de particules de graphite ou de coke. Un ensemble de matières carbonées sous-fluorées a une composition chimique moyenne CFx dans laquelle 0,63<x ≤0,95, 0,66<x ≤0,95 ou 0,7<x ≤0,95. Ces matières peuvent avoir une performance électrochimique supérieure au CF du commerce à des taux de décharge élevés.
PCT/US2007/062518 2006-02-21 2007-02-21 Électrochimie de sous-fluorures de carbone WO2007098478A2 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011010416A1 (fr) * 2009-07-21 2011-01-27 パナソニック株式会社 Batterie primaire au lithium
FR2999340A1 (fr) * 2012-12-12 2014-06-13 Univ Blaise Pascal Clermont Ferrand Ii Utilisation de nanoobjets en carbone sous fluore comme materiau d'electrode de batteries primaires au lithium de fortes capacites
US9812264B2 (en) 2012-04-16 2017-11-07 Panasonic Corporation Electrochemical energy storage device which exhibits capacity through a conversion reaction, and active material for the same and production method thereof
US10153491B2 (en) 2013-12-26 2018-12-11 Kyoto University Secondary battery
US10566624B2 (en) 2014-07-17 2020-02-18 Ada Technologies, Inc. Extreme long life, high energy density batteries and method of making and using the same
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Publication number Priority date Publication date Assignee Title
US8377586B2 (en) 2005-10-05 2013-02-19 California Institute Of Technology Fluoride ion electrochemical cell
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JP6783505B2 (ja) * 2014-07-18 2020-11-11 積水化学工業株式会社 薄片化黒鉛、電極材料及び薄片化黒鉛−樹脂複合材料
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4438086A (en) * 1981-09-02 1984-03-20 Central Glass Company Limited Method for preparation of graphite fluoride by contact reaction between carbon and fluorine gas
US5116592A (en) * 1986-06-02 1992-05-26 The Electrosynthesis Company, Inc. Fluorinated carbons and uses thereof
US5702844A (en) * 1995-03-03 1997-12-30 Saft Nickel electrode for an alkaline storage cell
US6068921A (en) * 1992-11-06 2000-05-30 Daikin Industries, Ltd. Carbon fluoride particles, preparation process and users of the same
US6358649B1 (en) * 1996-04-26 2002-03-19 Centre National De La Recherche Scientifique Carbons containing fluorine, method of preparation thereof and use as electrode material
FR2856674A1 (fr) * 2003-06-27 2004-12-31 Centre Nat Rech Scient Carbone fluore, procede pour son obtention

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4681823A (en) * 1986-05-19 1987-07-21 Allied Corporation Lithium/fluorinated carbon battery with no voltage delay

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4438086A (en) * 1981-09-02 1984-03-20 Central Glass Company Limited Method for preparation of graphite fluoride by contact reaction between carbon and fluorine gas
US5116592A (en) * 1986-06-02 1992-05-26 The Electrosynthesis Company, Inc. Fluorinated carbons and uses thereof
US6068921A (en) * 1992-11-06 2000-05-30 Daikin Industries, Ltd. Carbon fluoride particles, preparation process and users of the same
US5702844A (en) * 1995-03-03 1997-12-30 Saft Nickel electrode for an alkaline storage cell
US6358649B1 (en) * 1996-04-26 2002-03-19 Centre National De La Recherche Scientifique Carbons containing fluorine, method of preparation thereof and use as electrode material
FR2856674A1 (fr) * 2003-06-27 2004-12-31 Centre Nat Rech Scient Carbone fluore, procede pour son obtention

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011010416A1 (fr) * 2009-07-21 2011-01-27 パナソニック株式会社 Batterie primaire au lithium
US9812264B2 (en) 2012-04-16 2017-11-07 Panasonic Corporation Electrochemical energy storage device which exhibits capacity through a conversion reaction, and active material for the same and production method thereof
FR2999340A1 (fr) * 2012-12-12 2014-06-13 Univ Blaise Pascal Clermont Ferrand Ii Utilisation de nanoobjets en carbone sous fluore comme materiau d'electrode de batteries primaires au lithium de fortes capacites
WO2014091422A1 (fr) 2012-12-12 2014-06-19 Universite Blaise Pascal-Clermont-Ferrand Ii Utilisation de nanoobjets en carbone sous fluore comme matériau d'électrode de batteries primaires au lithium de fortes capacités
CN104885263A (zh) * 2012-12-12 2015-09-02 克莱蒙费朗第二大学 亚氟化的碳纳米物体作为具有强的容量的原锂电池的电极材料的用途
US9705133B2 (en) 2012-12-12 2017-07-11 Universite Blaise Pascal-Clermont-Ferrand Ii Use of subfluorinated carbon nano-objects as an electrode material of primary lithium batteries with strong capabilities
RU2636485C2 (ru) * 2012-12-12 2017-11-23 Юниверсите Блез Паскаль-Клермон-Ферран Ii Применение нанообъектов из не полностью фторированного углерода в качестве электродного материала для первичных литиевых элементов большой емкости
US10153491B2 (en) 2013-12-26 2018-12-11 Kyoto University Secondary battery
US10566624B2 (en) 2014-07-17 2020-02-18 Ada Technologies, Inc. Extreme long life, high energy density batteries and method of making and using the same
US11271205B2 (en) 2014-07-17 2022-03-08 Ada Technologies, Inc. Extreme long life, high energy density batteries and method of making and using the same
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WO2007098478A3 (fr) 2007-12-27
JP2009527441A (ja) 2009-07-30
CN101390234A (zh) 2009-03-18
WO2007098478A9 (fr) 2008-08-28
EP1999812A2 (fr) 2008-12-10
KR20080095909A (ko) 2008-10-29

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