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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y40/00—Manufacture or treatment of nanostructures
• • 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
  • C01B32/15—Nano-sized carbon materials
• • 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
  • C01B32/15—Nano-sized carbon materials
  • C01B32/152—Fullerenes
  • C01B32/156—After-treatment
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B1/00—Electrolytic production of inorganic compounds or non-metals
  • C25B1/01—Products
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B1/00—Electrolytic production of inorganic compounds or non-metals
  • C25B1/01—Products
  • C25B1/14—Alkali metal compounds
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B3/00—Electrolytic production of organic compounds
  • C25B3/01—Products
  • C25B3/03—Acyclic or carbocyclic hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B3/00—Electrolytic production of organic compounds
  • C25B3/01—Products
  • C25B3/09—Nitrogen containing compounds
• • 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
  • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
• • 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

• the present invention relates to novel salts of fullerenes, also known as fulleride salts, their preparation and use.
• Fullerenes are hollow molecules composed only of carbon atoms and constitute a new allotropic form of carbon. Typically, fullerenes each have carbon atoms arranged as 12 pentagons, but differing numbers of hexagons having the formula C2n where n is equal to or greater than 16 (hereinafter “fullerenes”). The pentagons are required in order to allow the curvature and eventual closure of the closed surface upon itself.
• the most abundant species of fullerenes identified to date is the C60 molecule or Buck insterfullerene (here ⁇ inafter "C6 ⁇ "). C60 consists of 12 pentagons and 20 hexagons. However, other species, including C70 have also been identified.
• Preferred monovalent cations include ammonium cations, alkyl ammonium cations such as quater ⁇ nary ammonium cations, alkali metal cations, phosphonium and arsoniu cations, especially organophosphonium and organoarsonium ions, partic ⁇ ularly phenylphosphonium and phenylarsonium cations.
• the preferred fullerene used in the practice of the present invention is C60-
• the fulleride salt compounds of the present invention are prepared by passing an electric current through (electrolyzing) a non-aqueous solution of fullerenes in the presence of a soluble salt containing a cation, A, of the A n C ⁇ compound to be formed. The electric potential is applied for a time sufficient to generate fullerene anions in the solution.
• the fulleride salt compounds are prepared in the solid state. The compounds of the present invention exhibit reversible electrochemical reduction; and, consequently, are particularly useful as electrode components in electrochemical cells such as secondary batteries.
• the fullerene anions, Ceo'- ⁇ and C70 ⁇ y, wherein y is a charge of from 1 to 3, specifically 1, 2, and 3 in the compound of the present invention contain unpaired electrons and thus have paramag ⁇ netic properties.
• C6o ⁇ l and C ⁇ o---- these properties are confirmed by electron spin resonance spectroscopy ("ESR") for the tetralkyl ammonium fulleride salt containing the C60 ⁇ * monoanion.
• ESR electron spin resonance spectroscopy
• the magnitude of the magnetic susceptibility of the compound of the present invention varies with the temperature accord ⁇ ing to the Curie-Weiss law, which is known to one having ordinary skill in the art. Since a one-to-one magnetic susceptibility tempera ⁇ ture correspondence exists, these compounds may be used as magnetic thermometers.
• fulleride salts containing C60" 1 monoanions may be used as semiconductors (See P. M. Allemand et al., J. Am. Chem. Soc., 113,2780 (1991)) while those containing C60" 3 and alkali-metals may be used as superconductors (See A. F. Hebard et al., Nature 350,600 (1991)).
• Alkali salts of C60 also can serve as starting materials for the preparation of other materials.
• the reaction of the lithium salt of Ceo, for example, with alkyl halides yield alkyl derivatives of fullerenes (See J. W. Bausch et al., J. Am. Che . Soc 113,3205 (1991)) that may be useful as polymer blends, composites and building blocks.
• the A n C x fulleride salts are stable in the absence of air and other reactive molecules. Their free radical character may make them suitable as spin labels.
• Spin labels are usually organic molecules that contain an unpaired electron (for example, a nitroxyl radical) and are used to render diamagnetic molecules to which they are attached susceptible to analysis by magnetic spin resonance techniques.
• the A n C x spin labels mixed, for example with polymers, may allow valuable information concerning polymer dynamics and struc ⁇ tures to be obtained.
• the present invention encompasses novel compositions of matter having the formula A n C x , wherein C x is a fullerene anion, wherein C x is preferably selected from the group consisting of C ⁇ o and C70, wherein A is a monovalent cation and wherein n is an integer from 1 to 3 inclusive, specifically 1, 2, and 3.
• the cation, A may be selected from a wide range of cations.
• the fullerene anion is further selected from the group consisting of monovalent, divalent and tri- valent anions. Its valence, however, depends on the formula of the monovalent cation, A n .
• C x will be a monovalent anion; where A n has the formula (A+l)2, C x will be a divalent anion; for (A+l)3, C x will be a trivalent anion.
• Particularly preferred cations for A include ammonium and alkyl ammonium cations, organophosphoniu or organoarsonium cations, especially tetraorganophosphoniu and tetra- organoarsonium ions, such as tetraphenylphosphonium and tetraphenyl- arsonium cations, alkali metal cations, and the like.
• the alkali metal cations Li, Na and K are especially preferred.
• the preferred fullerene used in the practice of the present invention is C60-
• the starting materials for the practice of the present invention can be obtained from commercial sources.
• the fullerenes may be prepared by graphite volatilization (see W. Kratschmer, et al, Nature. 347, p. 354 (1990)).
• Non-aqueous as used herein means solvent systems wherein water, if present, is electrochemically and chemically inert.
• toluene, dichloromethane in the case where the cation, A, is organic and a high polarity solvent such as dimethyl sulfoxide when the cation A is inorganic.
• a high polarity solvent such as dimethyl sulfoxide when the cation A is inorganic.
• Single, binary or multicomponent mixtures of tetrahy- drofuran, ethylene chloride, toluene, xylenes, dimethyl sulfoxide, dichloromethane, benzene are particularly suitable for dissolving the fullerenes.
• the salt containing the cation, A, of desired compound, A n C x must have some solubility in the organic solvent system used.
• salts containing organo groups such as, but not restricted to, R4NCI, R4ASU, R4PCI, R4NPF6, and R4NBF4 are particularly suitable.
• R is selected from the group consisting of hydrogen and an organic moiety.
• the organic moiety should be chosen in order to render the salt soluble in the solvent system. It is within the skill of one of ordinary skill in the art to make a selection of the appropriate solvent system.
• R may, for example, be selected from alkyl groups having from 1 to 16 carbon atoms and phenyl groups.
• Other useful salts include alkali metal salts having anions containing sufficient organic moieties to render the salt soluble in the solvent system.
• Representative examples include NaBPh4, KBPh4 where ("Ph” as used herein means phenyl or substituted phenyl group).
• the solvent system is more polar.
• Inorganic salts such as NaBF4, KC1 and KBr should be used with mixtures of tetrahydrofuran, dimethyl sulfoxide, dimethyl formamide, toluene and the like.
• the relative ratio of components of the solvent mixtures should be such as to insure some degree of solubility of both starting materials; i.e., fullerenes (which are soluble in relatively non-polar solvents) and inorganic salts (more soluble in polar sol ⁇ vents like dimethyl sulfoxide).
• a commercially available PAR (Princeton Applied Research) System equipped with Pt wire auxiliary electrode, standard calomel reference electrode (SCE) and a Pt gauze working electrode may be used to reduce, for example, up to gram quantities of the particular fullerene. Other commercial units may be used to prepare larger quantities of fulleride salts.
• a potentiostat regulates the potential necessary to produce the desired reduction state (salt of anion) of the fullerene in the particular solvent system.
• the molar ratio of salt to fullerene used in the solvent system will be generally greater than 3:1 and, preferably, will be in the range of about 10 to 20.
• the potential may be applied using any known source of direct current after immersing the working and reference electrodes into the solvent system.
• the auxiliary electrode may be isolated from the working electrode compartment during application of the electric potential, the mixture may be stirred, but such is not necessary.
• the reaction takes place at room temperature and pressure under a blanket of inert gas.
• an inert gas for example, N2, Ar
• N2 inert gas
• a potential of -0.45 V versus SCE in the DMSO solvent system using KBr as supporting electrolyte resulted in production of only the fullerene salts containing C60 monoanion. Since the potential necessary to produce the anions of desired valence is solvent dependent its value can be determined via cyclic volta - metry (CV) or differential pulse polarography (DPP). Care must be 6 -
• the process of the present invention may be used to selec ⁇ tively generate the salt of the fullerene anions in solutions of the fullerenes and other hydrocarbons by applying a current to the solu ⁇ tion, wherein the current is of sufficiently low voltage to selective ⁇ ly reduce the particular fullerene to the correspondent salt of the fullerene anion without reducing the other hydrocarbons.
• the fuller ⁇ ene anions have the formula C ⁇ -y, wherein C x is a fullerene, prefera ⁇ bly a fullerene selected from the group consisting of C ⁇ o and C70 and wherein y is an integer of from 1 to 3, specifically 1, 2 and 3.
• the range of electric potentials will vary with the solvent system, but can readily be selected by one having ordinary skill in the art.
• the electric potential is from about zero to about -0.7 V, when the fullerene anion is selected from the group consisting of C6o ⁇ l (when the fullerene is Ceo) and C70" 1 when the fullerene is C70; it is from about -0.80 V to about -1.1 V when the fullerene anion is selected from the group consisting of C ⁇ "2 (when the fullerene is C ⁇ o) and C7o * 2 (when the fullerene is C60) and C7o ⁇ 2 (when the fullerene is C70); and it is from about -1.3 V to about -1.7 V when the fullerene anion is selected from the group consisting of C ⁇ O" 3 (when the fuller ⁇ ene is C ⁇ o) and Z ⁇ ⁇ (when the fullerene is C70).
• 60 ⁇ l > which is prepared from C ⁇ o at a potential of -0.70 V in 1:2 dichloromethane/toluene mixtures, may be selectively prepared as the salt of the C60 ⁇ l anion from mixtures of C60 with other hydrocarbons having higher potentials (that is, having a chemical inertness within the range of potentials at which the C ⁇ o" 1 anion is produced) by applying the foregoing chemical potentials to the solution.
• the salt of the fullerene anion may be present in the solution or precipitated therefrom.
• the actual voltage may vary, depending on the solvent in which the reduction is conducted.
• the potential should be chosen within the range of the electrochemical potential necessary to generate the particular salt of the fullerene anion and within the range of chemical inertness for the other hydrocarbons. (For techni ⁇ cal details see, for example, P. T. Kissinger and Wm. H. Heine an, Editors, Laboratory Techniques in Electrochemistry-, Marcel Decker, Inc., N.Y. (1984); and A. Bard and L. Faulkner, Electrochemical Methods. Wiley and Sons, N.Y. (1980)).
• the A n C product may be isolated by precipitation; for example, using a non-solvent or precipitating agent, such as toluene or ether or by reducing the volume of the solvent used via vacuum distillation or low temperature freezing.
• a non-solvent or precipitating agent such as toluene or ether
• reducing the volume of the solvent used via vacuum distillation or low temperature freezing Using this technique, only the fullerene salt precipitates.
• KC1 is used as a source of potassium cation, only KC ⁇ n, not KC1 is precipitated. Only traces of chloride ions are detectable in the KC60 solid precipitate via scanning electron microscopy energy dispersive spectra technique.
• the following examples are intended to demonstrate the invention and not l imit it in any way.
• Example 1 The procedure specified in Example 1 was employed using C70 and produced the alkylammonium C70 *1 fulleride salt (Bu4N)+lC70" 1 , as shown by electrochemical and ESR analysis.
• a polar solvent system consisting of a dimethyl sulfoxide DMSO/toluene solution (6/1 v/v) containing a suspension of 0.1 g C ⁇ o and 0.25 KC1 was electrolyzed at -0.45 V vs. SCE for a time sufficient to produce C60 ⁇ *- The solution turned red at the end of the reduc ⁇ tion. Addition of toluene (about 5:1 toluene/DMSO) and refrigeration overnight at -20°C allowed for the removal of most of DMSO and some toluene as a frozen solid.
• Example 4 The procedure of Example 4 was repeated using KBr instead of KC1 to produce K+1C60 "1 fulleride salt.
• This example illustrates the use of C ⁇ O as a solid state electrode component.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
• Nanotechnology (AREA)
• Inorganic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Metallurgy (AREA)
• Physics & Mathematics (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• General Physics & Mathematics (AREA)
• Crystallography & Structural Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Composite Materials (AREA)
• Manufacturing & Machinery (AREA)
• Carbon And Carbon Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)

Applications Claiming Priority (3)

Publications (2)

Family

ID=25173281

Family Applications (1)

Country Status (5)

Families Citing this family (10)

• 1992
  • 1992-11-23 EP EP93900639A patent/EP0614444A4/de not_active Withdrawn
  • 1992-11-23 AU AU32230/93A patent/AU3223093A/en not_active Abandoned
  • 1992-11-23 CA CA002124191A patent/CA2124191A1/en not_active Abandoned
  • 1992-11-23 JP JP5510208A patent/JPH07501782A/ja active Pending
  • 1992-11-23 WO PCT/US1992/010120 patent/WO1993011067A1/en not_active Ceased

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events