EP2826085A1 - Matériaux composites, leur fabrication et leur utilisation dans des cellules électrochimiques - Google Patents

Matériaux composites, leur fabrication et leur utilisation dans des cellules électrochimiques

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Publication number
EP2826085A1
EP2826085A1 EP13761297.4A EP13761297A EP2826085A1 EP 2826085 A1 EP2826085 A1 EP 2826085A1 EP 13761297 A EP13761297 A EP 13761297A EP 2826085 A1 EP2826085 A1 EP 2826085A1
Authority
EP
European Patent Office
Prior art keywords
starting components
mixture
thermal treatment
sulfur
carbon
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Withdrawn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
EP13761297.4A
Other languages
German (de)
English (en)
Other versions
EP2826085A4 (fr
Inventor
Klaus Leitner
Alexander Panchenko
Oliver Gronwald
Arnd Garsuch
Heino Sommer
Norbert Bischof
Andrea KREBS
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP13761297.4A priority Critical patent/EP2826085A4/fr
Publication of EP2826085A1 publication Critical patent/EP2826085A1/fr
Publication of EP2826085A4 publication Critical patent/EP2826085A4/fr
Withdrawn legal-status Critical Current

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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
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to new composite materials, in their preparation as starting components at least
  • a thermally treated in a process step mixture comprising the starting components (A) and (B) or the starting components (A) and (C) or the starting components (A), (B) and (C), wherein the proportion of Sum of the proportions by weight of the starting components (A) and (B), (A) and (C) or (A), (B) and (C) in the respective mixture before the thermal treatment based on the total weight of the mixture before the thermal treatment 90 to 100 wt .-%, and wherein the thermal treatment of the mixture containing the starting components (A) and (B), (A) and (C) or (A), (B) and
  • the present invention also relates to a method for producing composite materials according to the invention, cathode materials for electrochemical cells comprising composite materials according to the invention, corresponding electrochemical cells and special thermally treated mixtures comprising at least the starting components (A) and (C).
  • Electrochemical cells such as batteries or accumulators, can be used to store electrical energy.
  • batteries or accumulators can be used to store electrical energy.
  • lithium-ion batteries are superior in some technical aspects to conventional batteries. So you can create with them voltages that are not accessible with batteries based on aqueous electrolytes.
  • lithium-ion secondary batteries having a carbon anode and a metal oxide-based cathode are limited in their energy density. New dimensions in energy density were opened by lithium-sulfur cells.
  • sulfur in the sulfur cathode is reduced via polysulfide ions to S 2_ , which are oxidized again during charging of the cell to form sulfur-sulfur bonds. Accordingly, during the charging and discharging processes, the structure of the cathode changes, which corresponds macroscopically to an expansion or shrinkage, that is to say a volume change, to the cathode.
  • the cathode in a lithium-sulfur cell usually contains carbon black or carbon black mixtures and binders.
  • the binders customarily contained in the cathodes of lithium-sulfur cells serve, on the one hand, to contact the soot particles, which are electrically conductive, with the electrochemically active sulfur, which itself is not electrically conductive, and, on the other hand, to connect the sulfur-carbon black mixture to the dissipative gas.
  • Materials of the cathode such as metal foils, metal nets or metal-coated plastic films.
  • Possible binders which are usually organic polymers, as well as the chemical and physical properties of the binders are known in principle to the person skilled in the art.
  • CN 101453009 describes the use of polylactic acid as a binder in cathodes for lithium-sulfur cells.
  • KR 2005087977 describes the use of carboxymethylcellulose (CMC) as a binder in cathode materials used in the construction of lithium-sulfur batteries.
  • US 2004/0009397 describes various fluorinated or partially fluorinated polymers or copolymers, in particular together with styrene-butadiene rubbers, as binders in cathode materials for lithium-sulfur batteries.
  • polyvinyl alcohol is used as a binder for the production of cathodes for lithium-sulfur cells.
  • WO 201 1/148357 describes sulfur-containing composite materials for cathodes which are obtained by thermal reaction of polyacrylonitrile, sulfur and carbon black.
  • the sulfur-containing cathode materials described in the literature still have deficits with regard to one or more of the properties desired for cathode materials or the electrochemical cells produced therefrom. Desirable are, for example, good adhesion of the cathode materials to the dissipative materials, high electrical conductivity of the cathode materials, an increase in cathode capacitance, an increase in the life of the electrochemical cell, improved mechanical stability of the cathode or a reduced volume change of the cathodes during one Charge-discharge cycle.
  • the aforementioned desired properties also contribute significantly to improving the efficiency of the electrochemical cell, which is in addition to the aspect of the desired technical performance profile of an electrochemical cell for the user of crucial importance.
  • Thodenmaterials has advantages, in particular a cathode material, which allows the construction of cathodes with improved electrical conductivity coupled with high cathode capacity, with high mechanical stability and long life.
  • This object is achieved by a composite material, in its production as starting components at least
  • the composite materials according to the invention are composite materials.
  • Composite materials are generally understood to mean materials which are solid mixtures which can not be separated manually and which have different properties than the individual components. Specifically, the composite materials of the invention are particle composites.
  • component (A) which is at least one fluorine-containing polymer, hereinafter also briefly called polymer (A)
  • component (B) wherein it is carbon in a modification which comprises at least 60% sp 2 -hybridised carbon atoms, hereinafter also referred to as carbon (B)
  • component (C) which is at least one sulfur-containing component, hereinafter also called component (C) for short.
  • the composite material according to the invention comprises a thermally treated mixture comprising the starting components (A) and (B) or the starting components (A) and (C) or the starting components (A), (B) and (C), in particular the starting components ( A), (B) and (C), wherein the proportion of the sum of the weight proportions of the starting components (A) and (B), (A) and (C) or (A), (B) and (C), in particular (A), (B) and (C), in the respective mixture before the thermal see treatment based on the total weight of the mixture before the thermal treatment 90 to 100 wt .-%, in particular 95 to 100 wt .-% is.
  • the polymer (A), that is to say the starting component (A), is at least one fluorine-containing polymer, the skilled worker being aware of numerous representatives of this class of polymer.
  • polymer (A) may also be a mixture of two or more fluorine-containing polymers.
  • polymer (A) is a fluorine-containing polymer.
  • the fluorine-containing polymers may be perfluorinated or partially fluorinated polymers or fluorine-containing homo- or copolymers.
  • polymer (A) from the group of fluorine-containing polymers consisting of polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkylvinyl ether copolymers, ethylene Tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers and ethylene-chlorofluoroethylene copolymers.
  • fluorine-containing polymers consisting of polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride
  • the polymer (A) is used in powder form. Particular preference is given to using a powder having an average particle size of 0.1 to 10 ⁇ m, in particular 0.5 to 2 ⁇ m.
  • polytetrafluoroethylene is understood to mean not only polytetrafluoroethylene homopolymers, but also copolymers of tetrafluoroethylene with hexafluoropropylene or vinylidene fluoride, and terpolymers consisting of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride.
  • Polymer (A) is preferably polytetrafluoroethylene, in particular polytetrafluoroethylene homopolymer.
  • the composite material according to the invention is characterized in that the fluorine-containing polymer is polytetrafluoroethylene, in particular polytetrafluoroethylene homopolymer.
  • Carbon in a modification which comprises at least 60% sp 2 -hybridized C atoms, preferably from 75% to 100% sp 2 -hybridized C atoms, also referred to as carbon (B) in the context of the present invention, is known as such .
  • the carbon (B) is an electrically conductive modification of carbon.
  • carbon (B) may be selected from graphite, carbon black, activated carbon, carbon nanotubes, carbon nanofibers, graphene, or mixtures of at least two of the foregoing.
  • data in% refers to the total carbon (B) used in the production of the composite material according to the invention, including any impurities, and denotes percent by weight.
  • carbon (B) is carbon black.
  • Carbon black may, for example, be chosen from lampblack, furnace black, flame black, thermal black, acetylene black, carbon black and furnace carbon black.
  • Carbon black may contain impurities, for example hydrocarbons, in particular aromatic hydrocarbons, or oxygen-containing compounds or oxygen-containing groups, for example OH groups.
  • sulfur or iron-containing impurities in carbon black are possible.
  • the composite material according to the invention is characterized in that carbon (B) is selected from carbon black.
  • carbon (B) is partially oxidized carbon black.
  • carbon (B) is carbon nanotubes.
  • Carbon nanotubes carbon nanotubes, in short CNT or English carbon nanotubes), for example single-walled carbon nanotubes (SW CNT) and preferably multi-walled carbon nanotubes (MW CNT), are known per se , A process for their preparation and some properties are described, for example, by A. Jess et al. in Chemie Ingenieurtechnik 2006, 78, 94 - 100.
  • carbon nanotubes have a diameter in the range of 0.4 to 50 nm, preferably 1 to 25 nm.
  • carbon nanotubes have a length in the range of 10 nm to 1 mm, preferably 100 nm to 500 nm.
  • Carbon nanotubes can be prepared by methods known per se. For example, one can use a volatile carbon-containing compound such as methane or carbon monoxide, acetylene or ethylene, or a mixture of volatile carbon-containing compounds such as synthesis gas in the presence of one or more reducing agents such as hydrogen and / or another gas such as nitrogen decompose. Another suitable gas mixture is a mixture of carbon monoxide with ethylene.
  • Suitable decomposition temperatures are, for example, in the range from 400 to 1000.degree. C., preferably from 500 to 800.degree.
  • Suitable pressure conditions for the decomposition are, for example, in the range of atmospheric pressure to 100 bar, preferably up to 10 bar.
  • Single- or multi-walled carbon nanotubes can be obtained, for example, by decomposition of carbon-containing compounds in the arc, in the presence or absence of a decomposition catalyst.
  • the decomposition of volatile carbon-containing compounds or carbon-containing compounds in the presence of a decomposition catalyst for example Fe, Co or preferably Ni.
  • carbon (B) is carbon nanofibers, in particular conductive, graphitized carbon nanofibers having a diameter in the range from 50 to 300 nm, preferably 70 to 200 nm and a length in the range from 1 ⁇ m to 100 ⁇ , preferably 2 ⁇ have up to 30 ⁇ .
  • Carbon nanofibers are commercially available, for example from the company carbon NT & F 21 ® .
  • graphene is understood as meaning almost ideal or ideally two-dimensional hexagonal carbon crystals, which are constructed analogously to individual graphite layers.
  • Carbon (B) may be present, for example, in particles having a diameter in the range of 0.1 to 100 ⁇ m, preferably 2 to 20 ⁇ m.
  • the particle diameter means the average diameter of the secondary particles, determined as volume average. The determination of the particle size distribution was carried out by means of laser diffraction technology in powder form with a mastersizer from Malvern Instruments GmbH, Berlinberg, Germany.
  • carbon (B) and especially carbon black have a BET surface area in the range of from 20 to 1500 m 2 / g as measured by ISO 9277.
  • at least two, for example two or three, are blended different types of carbon (B).
  • Different types of carbon (B) may differ, for example, in terms of particle diameter or BET surface area or level of contamination.
  • carbon (B) is selected from a combination of two different carbon blacks, in particular a combination of two different carbon blacks and carbon nanofibers.
  • At least one sulfur-containing component is used as component (C) in the production of the composite material according to the invention.
  • Sulfur-containing components contain sulfur in elemental form or bound in a chemical compound containing at least one sulfur atom.
  • the sulfur-containing component is selected from the group consisting of elemental sulfur, a composite prepared from elemental sulfur and at least one polymer, a polymer containing di- or di-polysulfide bridges and mixtures thereof.
  • the sulfur-containing component is elemental sulfur. Elemental sulfur is known as such.
  • Composites prepared from elemental sulfur and at least one polymer which are used as constituents of electrode materials are likewise known to the person skilled in the art.
  • a reaction product of sulfur and polyacrylonitrile is described, which is formed by hydrogen abstraction from polyacrylonitrile with simultaneous formation of hydrogen sulfide.
  • Polymers comprising divalent di- or polysulfide bridges such as, for example, polyethylene terephthalide, are also known in principle to a person skilled in the art.
  • divalent di- or polysulfide bridges such as, for example, polyethylene terephthalide
  • Polyorganodisulfides are used there as materials for solid redox polymerization electrodes in rechargeable cells together with polymeric electrolytes.
  • the composite material according to the invention is characterized in that the sulfur-containing component is elemental sulfur.
  • the composite material according to the invention comprises a mixture which has been thermally treated in one process step and which comprises the starting components (A) and (B) or the starting components (A) and (C) or the starting components (A), (B) and (C ) contains.
  • component (A) serves to mechanically bond the further components (B) and / or (C) together, that is to say component (A) serves to mechanically stabilize the composite material according to the invention.
  • the proportion by weight of the starting component (A) in the respective mixture before the thermal treatment based on the total weight of the mixture before the thermal treatment can in principle be varied within a wide range.
  • the composite material according to the invention is characterized in that the weight fraction of the starting component (A) in the respective mixture before the thermal treatment based on the total weight of the mixture before the thermal treatment is 4 to 1 1 wt .-%.
  • the proportion by weight of component (B) in the composite material according to the invention is preferably in the range from 1 to 60% by weight, particularly preferably in the range from 5 to 50% by weight, based on the total mass of the composite material.
  • the proportion of component (B) results from the amount used of this component based on the total mass of the composite material.
  • the starting components in the thermally treated mixture preferably in the preparation of the mixture of the starting components, they are homogeneously mixed with one another by appropriate mixing methods.
  • the composite material according to the invention is characterized in that before the step of the thermal treatment of the mixture in this mixture, the starting components (A) and (B), (A) and (C) or (A), (B ) and (C), in particular (A), (B) and (C), are homogeneously distributed.
  • the thermal treatment which is carried out at a temperature of at least 1 15 ° C, preferably the chemical nature of the starting materials used is not appreciably or not changed.
  • the thermal treatment of the mixture comprising the starting components (A) and (B), (A) and (C) or (A), (B) and (C), in particular (A), (B) and (C) be carried out in a wide temperature range, starting from at least 1 15 ° C, as long as no appreciable chemical reactions occur.
  • the thermal treatment of the mixture is preferably carried out at a temperature in the range from 120 to 500 ° C., more preferably from 150 to 400 ° C., in particular from 250 to 380 ° C.
  • the composite material according to the invention is characterized in that the thermal treatment of the mixture comprising the starting components (A) and (B), (A) and (C) or (A), (B) and (C) , in particular (A), (B) and (C), at a temperature in the range of 250 to 380 ° C takes place.
  • the thermal treatment is preferably carried out in a closed vessel in which pressure can build up, such as in an autoclave. In this way it is prevented that elemental sulfur at temperatures of at least 1 15 ° C can escape unhindered from the mixture.
  • the composite material according to the invention is characterized in that before the step of the thermal treatment of the mixture, this mixture of the starting components (A) and (B), (A) and (C) or (A), (B) and (C) has a hydrogen content of less than 0.5% by weight as determined by elemental analysis.
  • the above-described composite material of the present invention is particularly preferably selected from the starting materials polytetrafluoroethylene as component (A), carbon (B), which preferably has a carbon content of more than 95% by weight based on the total amount of carbon (B), and elemental sulfur Component (C) prepared, wherein the sum of the three starting components (A), (B) and (C) together is at least 95 wt .-%, preferably 98 to 100 wt .-% based on the total weight of the composite material. Accordingly, in the composite material according to the invention, the sum of the contents of the elements is preferably. Carbon, sulfur and fluorine are determined by elemental analysis to be at least 95% by weight, in particular at least 97% by weight up to 100% by weight.
  • the composite material according to the invention is characterized in that in the composite material, the sum of the contents of the elements carbon, sulfur and fluorine determined by elemental analysis is at least 95 wt .-%.
  • the composite material according to the invention has a sulfur content in the range from 20 to 80 wt .-%, preferably 37 to 70 wt .-%, which is determined by elemental analysis.
  • a method for producing the composite material according to the invention as described above comprises in each case a method step in which a mixture comprising the starting components (A) and (B), (A) and (C) or (A), (B) and ( C), in particular (A), (B) and (C), thermally treated at a temperature of at least 1 15 ° C.
  • the thermally treated mixture consists of 90 to 100 wt .-% of the corresponding starting components (A) and (B), (A) and (C) or (A), (B) and (C).
  • Another object of the present invention is a process for producing a composite material, in particular a composite material according to the invention as described above, comprising at least one process step, which is characterized in that one comprises a mixture containing starting components
  • (C) at least one sulfur-containing component, thermally treated at a temperature of at least 1 15 ° C, wherein the proportion of the sum of the weight proportions of the starting components (A) and (B), (A) and (C) or (A), ( B) and (C) in the respective mixture before the thermal treatment based on the total weight of the mixture before the thermal treatment is 90 to 100 wt .-%.
  • the description and preferred embodiments of the components (A), (B) and (C) in the method according to the invention are consistent with the above description of these components for the composite material according to the invention.
  • the thermal treatment of the mixture is preferably carried out at a temperature in the range from 120 to 500 ° C, particularly preferably from 150 to 400 ° C, in particular from 250 to 380 ° C.
  • the method according to the invention for producing a composite material is characterized in that the thermal treatment of the mixture comprising the starting components (A) and (B), (A) and (C) or (A), (B) and (C) at a temperature in the range of 250 to 380 ° C.
  • the duration for the thermal treatment of the mixture can vary within a wide range and, inter alia, also depends on the temperature at which thermal treatment is carried out.
  • the duration of the thermal treatment may be from 0.25 to 50 hours, preferably from 0.5 to 12 hours, especially from 1 to 5 hours.
  • the method according to the invention is suitable for producing composite technical materials in a continuous and / or discontinuous manner.
  • batch mode this means batch sizes over 10 kg, better> 100 kg, even better> 1000 kg or> 5000 kg.
  • continuous mode this means production volumes over 100 kg / day, better> 1000 kg / day, even more optimal> 10 t / day or> 50 t / day.
  • the composite materials according to the invention obtained in the process according to the invention are usually further converted into a pulverulent form by subsequent comminution steps known to those skilled in the art, which can finally be used as an essential component of cathode materials for electrochemical cells, in particular lithium-sulfur cells.
  • a further subject of the present invention is also a cathode material for an electrochemical cell, comprising at least one composite material according to the invention, as described above.
  • the cathode material according to the invention can furthermore comprise one or more binders, which are polymers as described, for example, in WO 201 1/148357, page 7, lines 5-25 and, if appropriate, further carbon (B), as previously described.
  • the cathode material according to the invention preferably contains at least 95% by weight, in particular between 97 and 100% by weight, of the composite material according to the invention. Ableitbleche and supply lines are not taken into account here.
  • Inventive composite materials and cathode materials according to the invention are particularly suitable as or for the production of cathodes, in particular for the production of cathodes of lithium-containing batteries.
  • the present invention relates to the use of composite materials according to the invention or cathode materials according to the invention as or for the production of cathodes for electrochemical cells.
  • Composite materials according to the invention or cathode materials according to the invention are furthermore distinguished by the fact that rechargeable electrochemical cells can be produced which preferably have at least 5 cycles, more preferably at least 10 cycles, very preferably at least 50 cycles, in particular at least 100 cycles or are stable over at least 150 cycles and in particular show a retention of the initial capacity of at least 80%.
  • that electrode is referred to as a cathode, which has a reducing effect during unloading (working).
  • composite material or cathode material according to the invention is processed into cathodes, for example in the form of endless bands, which are processed by the battery manufacturer.
  • cathodes produced from composite material or cathode material according to the invention may have thicknesses in the range from 20 to 500 ⁇ m, preferably 40 to 200 ⁇ m. They may be, for example, rod-shaped, in the form of round, elliptical or square columns or cuboidal or as flat cathodes.
  • the cathode according to the invention generally comprises electrical contacts for the supply and discharge of charges, for example a current conductor, in the form of a
  • Metal wire, metal mesh, metal mesh, expanded metal, or a metal foil or a metal sheet may be configured.
  • Aluminum foils are particularly suitable as metal foils.
  • a mixture of sulfur, carbon black and PTFE is coated on an aluminum foil and then thermally treated at 350 ° C for 1 to 5 hours to obtain a finished electrode. 2. Carbon black and PTFE are mixed and then thermally treated at 350 ° C for 1 to 5 hours. The thermally treated mixture is then mixed with sulfur and optionally thermally treated at 180 ° C for 1 to 5 hours or used directly. The composite material is used for the cathode preparation. 2a. A mixture of carbon black and PTFE is applied as a layer on an aluminum foil and then thermally treated at 350 ° C for 1 to 5 hours. Subsequently, sulfur is applied to the thermally treated layer (e.g., spraying or knife coating) and optionally thermally treated at 180 ° C for 1 to 5 hours or used directly as a cathode.
  • the thermally treated layer e.g., spraying or knife coating
  • Sulfur and PTFE are mixed and then thermally treated at 350 ° C for 1 to 5 hours.
  • the thermally treated mixture is then treated with carbon black mix and thermally treated at 350 ° C for 1 to 5 hours.
  • the formed composite material is used for the cathode preparation.
  • Another object of the present invention are electrochemical cells comprising at least one cathode, which was prepared from or using at least one composite material according to the invention or at least one cathode material according to the invention. Preference is thus given to electrochemical cells comprising at least one cathode which contains composite material according to the invention.
  • electrochemical cells according to the invention contain, in addition to the composite material or inventive cathode material, at least one electrode which contains metallic magnesium, metallic aluminum, metallic zinc, metallic sodium or preferably metallic lithium.
  • the electrochemical cell according to the invention is characterized in that it further contains at least one electrode containing metallic lithium.
  • the above-described electrochemical cells according to the invention comprise, in addition to the composite material according to the invention or the cathode material according to the invention, a liquid electrolyte which contains a lithium-containing conductive salt.
  • the electrochemical cell according to the invention is characterized in that it comprises a liquid electrolyte containing a lithium-containing conducting salt.
  • the above-described electrochemical cells according to the invention comprise, in addition to inventive composite material or inventive cathode material, and preferably another electrode, in particular an electrode containing metallic lithium, in particular at least one non-aqueous solvent which may be liquid or solid at room temperature, preferably liquid at room temperature is, and is preferably selected from polymers, cyclic or non-cyclic ethers, cyclic or non-cyclic acetals, cyclic or non-cyclic organic carbonates and ionic liquids.
  • the electrochemical cell according to the invention is characterized in that it comprises at least one nonaqueous solvent selected from polymers, cyclic or noncyclic ethers, noncyclic or cyclic acetals and cyclic or non-cyclic acetals. cyclic organic carbonates.
  • suitable polymers are in particular polyalkylene glycols, preferably P0IV-C1-C4-alkylene glycols and in particular polyethylene glycols.
  • Polyethylene glycols may contain up to 20 mol% of one or more C 1 -C 4 -alkylene glycols in copolymerized form.
  • Polyalkylene glycols are preferably polyalkylene glycols double-capped with methyl or ethyl.
  • the molecular weight M w of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be at least 400 g / mol.
  • the molecular weight M w of suitable polyalkylene glycols and in particular of suitable polyethylene glycols may be up to 5,000,000 g / mol, preferably up to 2,000,000 g / mol
  • non-cyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, preference is 1, 2-dimethoxyethane.
  • Suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.
  • non-cyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane and 1,1-diethoxyethane.
  • Suitable cyclic acetals are 1, 3-dioxane and in particular 1, 3-dioxolane.
  • non-cyclic organic carbonates examples include dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
  • Suitable cyclic organic carbonates are compounds of the general formulas (X) and (XI)
  • R 1 , R 2 and R 3 may be identical or different and selected from hydrogen and C 1 -C 4 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. Butyl and tert-butyl, preferably R 2 and R 3 are not both tert-butyl.
  • R 1 is methyl and R 2 and R 3 are each hydrogen or R 1 , R 2 and R 3 are each hydrogen.
  • the solvent (s) are preferably used in the so-called anhydrous state, ie with a water content in the range from 1 ppm to 0.1% by weight, determinable for example by Karl Fischer titration.
  • electrochemical cells according to the invention contain one or more conductive salts, preference being given to lithium salts.
  • suitable lithium salts are LiPF 6, LiBF 4, LiCI0 4, LiAsF 6, UCF3SO3, LiC (C n F 2n + IS02) 3, lithium imides such as LiN (C n F 2n + IS02) 2, where n is an integer in the range 1-20 LiN (SO 2 F) 2, Li 2 SiFe, LiSbF 6, LiAICU, and salts of the general formula (C n F 2n + i SO 2) m X Li, where m is defined as follows:
  • m 3 if X is chosen from carbon and silicon.
  • Preferred conductive salts are selected from LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , LiPF 6 , LiBF 4 , L1CIO 4 , and particularly preferred are LiPF 6 and LiN (CF 2 SO 2) 2.
  • electrochemical cells according to the invention contain one or more separators, by means of which the electrodes are mechanically separated.
  • Suitable separators are polymer films, in particular porous polymer films, which are unreactive with respect to metallic lithium and to lithium sulfides and lithium polysulfides.
  • Particularly suitable materials for separators are polyolefins, in particular film-shaped porous polyethylene and film-shaped porous polypropylene.
  • Polyolefin separators especially polyethylene or polypropylene, may have a porosity in the range of 35 to 45%. Suitable pore diameters are for example in the range from 30 to 500 nm.
  • separators made of PET particles filled with inorganic particles may have a porosity in the range of 40 to 55%. Suitable pore diameters are for example in the range of 80 to 750 nm.
  • the electrochemical cells of the invention can be assembled into lithium-ion batteries.
  • a further subject of the present invention is the use of inventive electrochemical cells, as described above, in lithium-ion batteries.
  • Another object of the present invention are lithium-ion batteries, in particular lithium-sulfur batteries, containing at least one inventive electrochemical see cell as described above.
  • inventive electrochemical cells can be combined with one another in lithium-ion batteries according to the invention, for example in series connection or in parallel connection. Series connection is preferred.
  • Electrochemical cells are characterized by particularly high capacity, high performance even after repeated charging and greatly delayed cell death. Electrochemical cells according to the invention are very well suited for use in automobiles, electric motor-operated two-wheelers, for example pedelecs, aircraft, ships or stationary energy storage devices. Such uses are a further subject of the present invention.
  • Another object of the present invention is the use of electrochemical cells according to the invention as described above in automobiles, electric motor-powered two-wheelers, aircraft, ships or stationary energy storage.
  • the use of lithium-ion batteries in devices according to the invention offers the advantage of a longer running time before recharging as well as a lower capacity loss with a longer running time. If one wanted to realize an equal running time with electrochemical cells with a lower energy density, then one would have to accept a higher weight for electrochemical cells.
  • Another object of the present invention is therefore also the use of lithium-ion batteries according to the invention in devices, in particular in mobile devices.
  • mobile devices are vehicles, for example automobiles, two-wheeled vehicles, aircraft or watercraft, such as boats or ships.
  • Other examples of mobile devices are ones that you move yourself, such as computers, especially laptops, phones or electrical
  • Hand tools for example from the field of construction, in particular drills, cordless screwdrivers or cordless tackers.
  • Another object of the present invention is also the use of a thermally treated mixture containing starting components at least one fluorine-containing polymer and (B) carbon in a modification comprising at least 60% sp 2 -hybridized C atoms, or (A) at least one fluorine-containing polymer and
  • (C) at least one sulfur-containing component, wherein the proportion of the sum of the weight proportions of the starting components (A) and (B), (A) and (C) or (A), (B) and (C) in the respective mixture before thermal treatment based on the total weight of the mixture before thermal treatment 90 to 100 wt .-%, and wherein the thermal treatment of the mixture containing the starting components (A) and (B), (A) and (C) or (A) , (B) and (C) is carried out at a temperature of at least 1 15 ° C, for producing an electrochemical cell, more preferably for producing an electrode for an electrochemical cell, most preferably for producing a cathode for an electrochemical cell, in particular for producing a sulfur cathode for a lithium-sulfur cell.
  • (C) at least one sulfur-containing component, wherein the proportion of the sum of the weight proportions of the starting components (A) and (C) or (A), (B) and (C) in the respective mixture before the thermal treatment based on the total weight of the mixture before the thermal treatment is 90 to 100 wt .-%, and wherein the thermal treatment of the mixture containing the starting components (A) and (C) or (A), (B) and (C) at a temperature of at least 1 15 ° C is performed.
  • the ink was sprayed by airbrush on a vacuum table (temperature: 75 ° C) on an aluminum foil (thickness: 30 ⁇ ). Nitrogen was used for spraying. After spraying, the coated film was then driven at 120 ° C through an office calender and then dried overnight at 40 ° C and 40 mbar. A sulfur loading of 1.2 mg / cm 2 was achieved.
  • the ink was sprayed by means of an airbrush method on a vacuum table (temperature: 75 ° C.) onto an aluminum foil (thickness: 30 ⁇ m). Nitrogen was used for spraying. After spraying, the coated film was then driven at 120 ° C through an office calender and then dried overnight at 40 ° C and 40 mbar. A solids loading of 1.2 mg / cm 2 was achieved.
  • Electrochemical cells according to FIG. 1 were built for the electrochemical characterization of cathodes K1, V-K2, K3 and V-K4 prepared in Example I. For this purpose, in each case the following components were used in addition to the cathodes produced in Example I.
  • Anode Li foil, 50 ⁇ thick,
  • Electrolyte 1 M LiTFSI (LiN (S0 2 CF 3 ) 2 in 1: 1 mixture of dioxolane and dimethoxyethane.
  • the electrochemical cells Z1 and Z3 according to the invention were produced, and the comparison electrodes V-K2 and V-K4 were used to construct the comparative electrochemical cells V-Z2 and V-Z4 not according to the invention.
  • FIG. 1 shows the schematic structure of a disassembled electrochemical cell for testing cathodes according to the invention and not according to the invention.
  • FIG. 1 The explanations in FIG. 1 mean:
  • Table 1 Test results of electrochemical cells according to the invention and not according to the invention.
  • Figure 2 shows the average charging and discharging voltages of the electrochemical cells E1 (solid lines) and V-E.2. The number of cycles is indicated on the x-axis and the voltage in volts on the y-axis.
  • the Li sulfur cell Z.1 according to the invention has significantly improved charging and discharging voltages than the comparison cell V-Z.2.
  • Z.1 shows a low voltage during charging (about 2.3 V) and a higher voltage during the discharging process (about 2.13 V) than V-Z.2.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne de nouveaux matériaux composites dans la fabrication desquels on utilise, comme composants de départ, au moins (A) au moins un polymère fluoré, (B) du carbone dans une modification qui contient au moins 60 % d'atomes de carbone hybridés en sp², et (C) au moins un composant soufré, qui comprend un mélange qui a subi un traitement thermique dans une étape de procédé et qui contient les composants de départ (A) et (B) ou les composants de départ (A) et (C) ou les composants de départ (A), (B) et (C), la fraction de la somme des parties en poids des composants de départ (A) et (B), (A) et (C) ou (A), (B) et (C) dans le mélange considéré avant le traitement thermique rapporté au poids total du mélange avant le traitement thermique étant de 90 à 100 % en poids, et le traitement thermique du mélange contenant les composants de départ (A) et (B), (A) et (C) ou (A), (B) et (C) étant conduit à une température d'au moins 115°C. La présente invention concerne également un procédé pour la production de matériaux composites selon l'invention, des matériaux de cathode pour cellules électrochimiques contenant des matériaux composites selon l'invention, des cellules électrochimiques correspondantes ainsi que des mélanges spéciaux traités thermiquement, contenant au moins les composants de départ (A) et (C).
EP13761297.4A 2012-03-14 2013-03-05 Matériaux composites, leur fabrication et leur utilisation dans des cellules électrochimiques Withdrawn EP2826085A4 (fr)

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US4261853A (en) * 1979-09-24 1981-04-14 Magnavox Government And Industrial Electronics Co. Deferred action battery having an improved depolarizer
JPS61190870A (ja) * 1985-02-19 1986-08-25 Showa Denko Kk 低嵩密度二硫化チタン電極の製造法
JP3624088B2 (ja) * 1998-01-30 2005-02-23 キヤノン株式会社 粉末材料、電極構造体、それらの製造方法、及びリチウム二次電池
WO1999065101A1 (fr) * 1998-06-08 1999-12-16 Moltech Corporation Monomeres multi-fonctionnels reactifs aux fins de la protection de cellules electrochimiques non aqueuses
JP3670931B2 (ja) * 2000-04-25 2005-07-13 三洋電機株式会社 リチウム二次電池用電極材料及びリチウム二次電池
KR101422311B1 (ko) * 2006-12-04 2014-07-22 시온 파워 코퍼레이션 전해질의 분리
JP5425107B2 (ja) * 2008-03-05 2014-02-26 イーグルピッチャー テクノロジーズ，エルエルシー リチウム−硫黄電池およびそのカソード
EP2228857A1 (fr) * 2009-03-06 2010-09-15 Basf Se Unités d'électrodes à membrane améliorées
JP5856609B2 (ja) * 2010-05-28 2016-02-10 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ リチウム硫黄電流生成セルの正極に使用される固体複合材料及びその製造方法並びにリチウム硫黄電流生成セル
DE102010030887A1 (de) * 2010-07-02 2012-01-05 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Kathodeneinheit für Alkalimetall-Schwefel-Batterie
CN103460445A (zh) * 2011-04-04 2013-12-18 巴斯夫欧洲公司 包含离子交换器的电化学电池
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WO2013136223A1 (fr) 2013-09-19
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CN104170128A (zh) 2014-11-26

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