Classifications

• • 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
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
• • 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
• • 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 a cathode material for a rechargeable battery with solid electrolyte, and to rechargeable batteries comprising said material as cathode material.
• Lithium batteries with soli electrolyte constitute a particularly interesting class of rechargeable batteries. These batteries include reversible lithium electrodes, one acting as a source of lithium ions during discharge, the other as a lithium ion receiver, the two being separated by a thin fi of polymer electrolyte acting as a support for 'io lithium. The process is reversed during recharging.
• the lithium source can be a sheet of metallic lithium (or of lithium alloy, a low-potential lithium ion insertion structure (for example W0 2 ) or a n-doped conjugated polymer with lithi (TiS 2 , v 6 ° i3 r Mo0 2 , etc.), a transiti metal compound reducible by lithium (for example FeS 2 , NiS 2 ) or p-doped conjugated polymer.
• the lithium ion support is obtained by dissolving a lithium salt (for example LiCl0 LiCF 3 S0 3 ) in a solvating aprotic polymer such as polyethylene oxide.
• cathode material various compounds for inserting lithium ions known as cathode material in non-rechargeable batteries.
• the cathode material is a carbon fluoride CF ⁇ obtained by the action of fluorine on graphite, at a temperature of the order of 350 to 650 ° C.
• Such a material is a carbon fluoride CF ⁇ obtained by the action of fluorine on graphite, at a temperature of the order of 350 to 650 ° C.
• REPLACEMENT SHEET cathode suitable for batteries the reversibility of the insertion of lithium ions into such a material is practically zero and it is not possible to use it in rechargeable batteries.
• the use as cathode material of carbon fluorides obtained at ambient temperature has been described, on the one hand, in solid polymer electrolyte cells, on the other hand, in an electrochemical liquid electrolyte system (carbonate propylene).
• the reversibility of the insertion of lithium ions has been found to be very poor in the liquid system.
• Solvan 0 contributes to entraining LiF formed outside the electochemically active zones, in particular outside of the electrolyte by dissolution and nucleation.
• electrochemical systems with solid electrolyte allow good reversibility of the insertion of lithium ions into a material constituted by a graphite fluoride obtained at ambient temperature, and they put developed a new solid rechargeable electrolyte battery.
• the subject of the present invention is a rechargeable battery comprising a solid polymer electrolyte, an anod constituted by a lithium source and a cathod comprising a lithium receptive material, characterized in that the lithium receptive material is a compound corresponding to the formula CF ⁇ M y , M being chosen from I, Cl, B Re, W, Mo, B, and 0.3 ⁇ x 0.9, 0.02 ⁇ y ⁇ 0.06, the structure of
• REPLACEMENT SHEET material being such that the carbon atoms form planar hexagons.
• the compounds which can be used as receptor materials so obtained at ambient temperature by reaction of graphite with gaseous fluorine F 2 , in the presence of an HF + MF n com catalyst mixture (n representing the valence of the element M). catalyst lowers the energy barrier for formation of CF bonds.
• MF n compounds which can be used in the present invention, mention may be made of IF 7 , I 5 , C1F 3 , BrF 5 , BF 3 , ReF 6 ReF 7 , WF 6 , M ⁇ F 6 .
• Particularly preferred compounds are IFy, IF 5 C1F 3 , BrF 5 , BF 3 and ReF 7 .
• IF 7 and IF 5 allow to obtain the highest fluorine content in the compound
• the electrolyte used in the battery according to the invention is a solid polymer electrolyte.
• a solid polymer o can use, for example, chemically inert compounds as described in particular in European patent 13199 e the French patent filed on 15.06.1983 under the number 8309886 Polyethers are particularly suitable.
• a particularly interesting material is polyethylene oxide containing a lithium salt, for example LiC10 4 or LiCF 3 S0 3 .
• a lithium salt for example LiC10 4 or LiCF 3 S0 3 .
• the cathode consists of a composite material comprising, in addition to the compound receiving lithium ions CF ⁇ M y , the material constituting the electrolyte.
• the materials conventionally used in lithium batteries can be used. Among them, mention may be made of metallic lithium or a lithium alloy, low-potency lithium insertion compounds.
• REPLACEMENT SHEET tiel in particular 0 2 or a n-doped lithium • conjugated polymer.
• MF n was then prepared by direct fluorination of the element M or of a salt of M.
• a steady stream of an F 2 + mixture was maintained in the reactor for several hours at room temperature.
• salts were used, among which mention may be made of KBr, KCl, NaB NaCl.
• the element M itself was used, for example I 2 , W or Mo.
• composition of the products obtained was determined by elementary analysis. A hydrogen content of less than 0.01% has been detected, which proves that HF does indeed act as a catalyst. Samples A to D were thus obtained.
• Table 1 gives the composition of the products CF_- obtained as a function of the starting product MF n -
• a battery was produced according to the following diagrams 5 Li / P (OE) 8 , LiC10 4 / CF 0 80 I 0 Q2 using material A.
• the battery consists of a high purity lithium disc having a thickness of approximately 0.5 mm and a diameter of approximately 17 mm. This lithium disc was pressed onto a stainless steel disc of the same diameter, constituting the electron collector.
• the thin film cathode é obtained by pulverizing a composite CF suspension Q 3 0 - ** O 02 'Phit g ra * e and PEO (polyethylene oxide in acetonitrile on a stainless steel disk 20 m ⁇ .S c in diameter.
• the cathode was then dried at room temperature under argon, then at 80 ° C under vacuum for several hours.
• the volume composition of the cathode was approximately 40% CF 0 80 I 0 02 , 10% graphite, 50% P (OE) 8 LiCl0 4 Its weight was approximately 10 mg.
• FIGS. 1 to 4 The reversibility of the system has been demonstrated by carrying out cyclovoltammograms at 80 "C with different scanning speeds represented in FIGS. 1 to 4.
• the scanning speed was 1 V respectively. / min, 100 mV / min, 10 mV / min and 1 mV / min.
• the intensity of the current (in A) is given as ordered, and the voltage (in Volts) of the Li-Li + system
• the scales, for the current intensities, are shown in the figures 5
• the peaks corresponding to oxidation, marked (1) have an area of the same order of magnitude as the peaks
• a battery was produced according to the following diagram:
• Li / P (OE) 8 LiC10 4 / CF Q 5 B 0 06 using the material according to sample D.
• the structure of the battery is identical to that of Example 1.
• the capacity measured on the battery obtained varies between 40 and 600 A.h / kg.
• a battery corresponding to the scheme Li / P (0E) 8 , LiC10 4 / CF Q 7 W 0 06 was produced according to the procedure of Example 1.
• the theoretical capacity of such a system is 620 A.h / kg e the measured capacity is of the order of 460 A.h / kg.
• (CF) n is a graphite fluoride obtained at high temperature
• FIGS. 5, 6, 7 and 8 The cyclovaltammograms, carried out at 80 "C with different scanning speeds and a mass of (CF) n equivalent to 1, times the mass of fluoride used in Example 1, are represented in FIGS. 5, 6, 7 and 8.
• the voltage (in volts) is plotted on the abscissa, and the current intensity (in A) on the ordinate.
• the scales for the current intensities are shown in the figures.
• the cyclovoltammogram is shown in FIG. 9.
• the voltage (in volts) is plotted on the abscissa and the current intensity (in mA) on the ordinate.
• (3) represent the first cycle, (4) the second, (5) the third and (6) twelfth. It can be seen that the cycles are not superimposable. Furthermore, in the first cycles, the p (2) corresponding to dormitor, the reduction is very clearly disproportionate compared to the peak (1) which corresponds to the oxidation.
• Such a system can therefore not be used to constitute a rechargeable battery.
• lithium electochemical systems associating graphite fluoride obtained at high temperature with solid polymer electrolyte, or graphi fluoride obtained at room temperature with liquid electrolyte constitute rechargeable batteries with good performance.

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• Chemical & Material Sciences (AREA)
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• General Chemical & Material Sciences (AREA)
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• Life Sciences & Earth Sciences (AREA)
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• Environmental & Geological Engineering (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
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• General Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
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• Battery Electrode And Active Subsutance (AREA)
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• 1988
  • 1988-12-26 FR FR8817172A patent/FR2641902B1/fr not_active Expired - Fee Related
• 1989
  • 1989-12-22 WO PCT/FR1989/000670 patent/WO1990007798A1/fr not_active Ceased
  • 1989-12-22 US US07/690,984 patent/US5175066A/en not_active Expired - Fee Related
  • 1989-12-22 JP JP2501750A patent/JPH04502533A/ja active Pending
  • 1989-12-22 EP EP90900890A patent/EP0449921A1/de not_active Withdrawn

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