EP2576682A1 - Matériaux composites, leur fabrication et leur utilisation dans des piles voltaïques - Google Patents

Matériaux composites, leur fabrication et leur utilisation dans des piles voltaïques

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Publication number
EP2576682A1
EP2576682A1 EP11786222.7A EP11786222A EP2576682A1 EP 2576682 A1 EP2576682 A1 EP 2576682A1 EP 11786222 A EP11786222 A EP 11786222A EP 2576682 A1 EP2576682 A1 EP 2576682A1
Authority
EP
European Patent Office
Prior art keywords
composite material
carbon
sulfur
polyacrylonitrile
organic polymer
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Withdrawn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
EP11786222.7A
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German (de)
English (en)
Other versions
EP2576682A4 (fr
Inventor
Nicole Janssen
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
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP11786222.7A priority Critical patent/EP2576682A4/fr
Publication of EP2576682A1 publication Critical patent/EP2576682A1/fr
Publication of EP2576682A4 publication Critical patent/EP2576682A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • 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
    • H01M10/052—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
    • 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
    • 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
    • H01M4/5815—Sulfides
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/604—Polymers containing aliphatic main chain polymers
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • 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

Definitions

  • the present invention relates to a composite material comprising a reaction product of
  • the present invention further relates to a process for producing inventive composite materials.
  • the present invention further relates to the use of inventive composite materials.
  • Secondary batteries or rechargeable batteries are just some embodiments by which electrical energy can be stored after generation and used (consumed) when required. Owing to the significantly better power density, there has been a departure in recent times from water-based secondary batteries to development of batteries in which the charge transport is accomplished by lithium ions.
  • lithium-sulfur cells sulfur in the sulfur cathode is reduced via polysulfide ions to S 2_ , which is reoxidized when the cell is charged.
  • a problem is the solubility of the polysulfides, for example L12S4 and L12S6, which are soluble in the solvent and can migrate to the anode.
  • the consequences may include: loss of capacitance and deposition of electrically insulating material on the sulfur particles of the electrode.
  • the migration from cathode to anode can ultimately lead to discharge of the affected cell and to cell death in the battery.
  • This unwanted migration of polysulfide ions is also referred to as "shuttling", a term which is also used in the context of the present invention.
  • inventive materials are composite materials, which are also referred to as inventive composite materials in the context of the present invention.
  • Composite materials are understood to mean materials which are solid mixtures which cannot be separated manually and which have different properties than the individual components.
  • inventive materials are, especially, particulate composite materials.
  • Inventive composite material comprises a reaction product of
  • polymer (A) at least one organic polymer, referred to as polymer (A) or organic polymer (A) for short, the expression polymer in the context of the present invention comprising homopolymers and also copolymers,
  • Polymer (A) can be selected from any organic polymers and copolymers, preferably from polymers obtainable by anionic or free-radical (co)polymerization.
  • polymer (A) can be selected from organic polyesters, especially from aliphatic polyesters.
  • polymer (A) is selected from (co)polymers obtainable by anionic, catalytic or free-radical (co)polymerization, especially from polyethylene, polyacrylonitrile, polybutadiene, polystyrene and copolymers of at least two comonomers selected from ethylene, propylene, styrene, (meth)acrylonitrile and 1 ,3- butadiene.
  • Polypropylene is also suitable.
  • Polyisoprene and polyacrylates are additionally suitable. Particular preference is given to polyacrylonitrile, also referred to as poly- acrylonitrile (A) in the context of the present invention.
  • polyacrylonitrile is not only understood to mean polyacrylonitrile homopolymers, but also copolymers of acrylonitrile with 1 ,3-butadiene or styrene. Preference is given to polyacrylonitrile homopolymers.
  • polyacrylonitrile (A) is present after the reaction, i.e. in the inventive composite material, at least partially in the form of a cycli- zation product of the formula (I)
  • polyethylene is understood to mean not only homopolyethylene but also copolymers of ethylene which comprise at least 50 mol% of ethylene in copolymerized form, and up to 50 mol% of at least one further comonomer, for example oolefins such as propylene, butylene (1 -butene), 1 -hexene, 1 -octene, 1 - decene, 1 -dodecene, 1 -pentene, and also isobutene, vinylaromatics, for example styrene, and also (meth)acrylic acid, vinyl acetate, vinyl propionate, Ci-Cio-alkyl esters of (meth)acrylic acid, especially methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-but
  • polypropylene is not only understood to mean homopolypropylene, but also copolymers of propylene which comprise at least
  • polystyrene is not only understood to mean ho- mopolymers of styrene, but also copolymers with acrylonitrile, 1 ,3-butadiene,
  • (meth)acrylic acid Ci-Cio-alkyl esters of (meth)acrylic acid, divinylbenzene, especially 1 ,3-divinylbenzene, 1 ,2-diphenylethylene and omethylstyrene.
  • Another preferred polymer (A) is polybutadiene.
  • polymer (A) is selected from those which, before the reaction, have a mean molecular weight M w in the range from 50 000 to 500 000 g/mol, preferably to 250 000 g/mol.
  • polyacrylonitrile (A) is selected from those polyacrylonitriles which, before the reaction, have a mean molecular weight M w in the range from 10 000 to 500 000 g/mol.
  • Polymer (A) may be crosslinked or uncrosslinked (co)polymers.
  • Sulfur (B) is known as such and can also be referred to for short as sulfur in the context of the present invention.
  • carbon (C) may be graphite.
  • carbon (C) is carbon black.
  • Carbon black may, for example, be selected from lamp black, furnace black, flame black, thermal black, acetylene black and industrial black.
  • Carbon black may comprise impurities, for example hydrocarbons, especially aromatic hydrocarbons, or oxygen-containing compounds or oxygen-containing groups, for example OH groups.
  • sulfur- or iron-containing impurities are possible in carbon black.
  • carbon (C) is partially oxidized carbon black.
  • carbon (C) comprises carbon nanotubes.
  • Carbon nanotubes (CNTs for short), for example single-wall carbon nanotubes, SW CNT) and preferably multiwall carbon nanotubes (MW CNT) are known per se.
  • a pro- cess for preparation thereof 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 from 0.4 to 50 nm, preferably 1 to 25 nm.
  • carbon nanotubes have a length in the range from 10 nm to 1 mm, preferably 100 nm to 500 nm.
  • Carbon nanotubes can be prepared by processes known per se.
  • a vola- tile carbon compound for example methane or carbon monoxide, acetylene or ethylene, or a mixture of volatile carbon compounds, for example synthesis gas
  • a vola- tile carbon compound for example methane or carbon monoxide, acetylene or ethylene, or a mixture of volatile carbon compounds, for example synthesis gas
  • reducing agents for example hydrogen and/or a further gas, for example nitrogen.
  • Another suitable gas mixture is a mixture of carbon monoxide with ethylene.
  • Suitable temperatures for decomposition are, for ex- ample, in the range from 400 to 1000°C, preferably 500 to 800°C.
  • Suitable pressure conditions for the decomposition are, for example, in the range from standard pressure to 100 bar, preferably to 10 bar.
  • Single- or multiwall carbon nanotubes can be obtained, for example, by decomposition of carbon-containing compounds in a light arc, specifically in the presence or absence of a decomposition catalyst.
  • the decomposition of volatile carbon-containing compound or carbon-containing compounds is performed in the presence of a decomposition catalyst, for example Fe, Co or preferably Ni.
  • a decomposition catalyst for example Fe, Co or preferably Ni.
  • At least two of the aforementioned starting materials have reacted chemically with one another in the course of preparation of inventive composite material, preferably polymer (A) and sulfur.
  • polymer (A) and sulfur it is not necessary that polymer (A) and sulfur have entered into covalent bonds with one another.
  • sulfur serves merely as an oxidizing agent and is removed from the reaction mixture as hbS.
  • polymer (A) and sulfur (B) have entered into covalent bonds in the course of formation of inventive composite material.
  • Inventive composite material further comprise particles or domains which comprise carbon (C) filled with sulfur (B).
  • sulfur is molecularly dispersed in carbon (C) in such particles or domains, for example in the form of Se rings or in the form of linear sulfur molecules, for example linear Ss mole- cules.
  • Such particles or domains can be detected, for example, by electron probe microanalysis.
  • the pores of carbon (C) in such particles or domains are at least partially filled with sulfur (B).
  • Such particles or domains may have a mean diameter in the range from 10 to 100 ⁇ , preferably to 70 ⁇ .
  • such particles or domains comprise carbon (C) and sulfur (B) in a weight ratio in the range from 2 : 1 to 1 : 15, preferably 1 : 1 .5 to 1 : 10.
  • Above-described particles or domains preferably appear black to the human eye.
  • above-described particles or domains comprise not more than 5% by weight of polymer (A) or not more than 5% by weight of above-described reaction product.
  • neither polymer (A) nor above-described reaction product can be detected in the above-described particles or domains.
  • Inventive composite material may further comprise particles or domains which comprise significant proportions of above-described reaction product, for example to an extent of at least 10% by weight.
  • the latter particles or domains may have a diameter in the range from 5 to 75 ⁇ , preferably 10 to 50 ⁇ . They are preferably smaller than the former particles or domains.
  • inventive composite material comprises in the range from 20 to 80% by weight, preferably 30 to 70% by weight, of sulfur, determined by elemental analysis. In one embodiment of the present invention, inventive composite material comprises in the range from 0.1 to 30% by weight of carbon (C), preferably 1 to 20% by weight. This carbon is likewise determinable, for example, by elemental analysis, though it must be taken into account in the evaluation of the elemental analysis that carbon also gets into inventive composite material via polymer (A). In one embodiment of the present invention, inventive composite material further comprises at least one binder (D). Binder (D) serves principally for mechanical stabilization of inventive composite material. In one embodiment of the present invention, binder (D) is selected from organic
  • (co)polymers examples include suitable organic (co)polymers.
  • suitable organic (co)polymers may be halogenated or halogen-free.
  • PEO polyethylene oxide
  • cellulose carboxymethylcellulose
  • polyvinyl alcohol polyethylene
  • polypropylene polytetrafluoroethylene
  • polyacryloni- trile-methyl methacrylate copolymers polyethylene
  • polypropylene polytetrafluoroethylene
  • polyacryloni- trile-methyl methacrylate copolymers styrene-butadiene copolymers, tetrafluoroethyl- ene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP)
  • PVdF-HFP vinylidene fluoride-tetrafluoroethylene copolymers
  • perfluoroalkyl vinyl ether copolymers
  • Suitable binders are especially polyvinyl alcohol and halogenated (co)polymers, for example polyvinyl chloride or polyvinylidene chloride, especially fluorinated
  • (co)polymers such as polyvinyl fluoride and especially polyvinylidene fluoride and polytetrafluoroethylene.
  • the mean molecular weight M w of binder (D) may be selected within wide limits, suit- able examples being 20 000 g/mol to 1 000 000 g/mol.
  • inventive composite material comprises in the range from 0.1 to 10% by weight of binder, preferably 5 to 10% by weight and more preferably 7 to 8% by weight.
  • Binder (D) can be incorporated into inventive composite material by various processes. For example, it is possible to dissolve soluble binders (D) such as polyvinyl alcohol in a suitable solvent or solvent mixture, water/isopropanol for example being suitable for polyvinyl alcohol, and to prepare a suspension with the further constituents of the cath- ode. After application to a suitable substrate, the solvent or solvent mixture is removed, for example evaporated, to obtain inventive composite material.
  • a suitable solvent for polyvinylidene fluoride is NMP.
  • inventive composite material additionally comprises carbon, which is incorporated into the composite material under nonreactive conditions.
  • This additional carbon may be selected from the same materials as carbon (C). It may in each case be the same as or different than carbon (C); for example, the carbon (C) and the additional carbon selected may be two different carbon blacks or graphites.
  • inventive composite material additionally comprises carbon black which has not been reacted with organic polymer (A) or poly- acrylonitrile (A) and sulfur (B).
  • inventive composite material comprises in the range from 0.1 to 10% by weight of additional carbon, preferably additional carbon black.
  • Inventive composite materials are particularly suitable as or for production of electrodes, especially for production of electrodes of lithium-containing batteries.
  • the present invention provides for the use of inventive composite materials as or for production of electrodes for electrical cells.
  • the present invention further provides electrical cells comprising at least one electrode which has been produced from or using at least one inventive composite material.
  • the electrode in question is the cathode, which can also be referred to as the sulfur cathode or S cathode.
  • the electrode referred to as the cathode is that which has reducing action on discharge (operation).
  • inventive composite material is processed to give electrodes, for example in the form of continuous belts which are processed by the battery manufacturer.
  • Electrodes produced from inventive composite material may, for example, have thicknesses in the range from 20 to 500 ⁇ , preferably 40 to 200 ⁇ . They may, for exam- pie, have a rod-shaped configuration, or be configured in the form of round, elliptical or square columns or in cuboidal form, or as flat electrodes.
  • inventive electrical cells comprise, as well as inventive composite material, at least one electrode which comprises metallic zinc, metallic sodium or preferably metallic lithium.
  • inventive electrical cells comprise, in addition to inventive composite material and a further electrode, at least one nonaqueous solvent which may be liquid or solid at room temperature, preferably selected from polymers, cyclic or noncyclic ethers, cyclic and noncyclic acetals, cyclic or noncyclic or- ganic carbonates and ionic liquids.
  • suitable polymers are especially polyalkylene glycols, preferably poly-Ci- C 4 -alkylene glycols and especially polyethylene glycols. These polyethylene glycols may comprise up to 20 mol% of one or more Ci-C 4 -alkylene glycols in copolymerized form.
  • the polyalkylene glycols are preferably polyalkylene glycols double-capped by 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 especially of suitable polyethylene glycols may be up to 5 000 000 g/mol, preferably up to 2 000 000 g/mol.
  • noncyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1 ,2-dimethoxyethane, 1 ,2-diethoxyethane, preference being given to 1 ,2- dimethoxyethane.
  • Suitable cyclic ethers are tetrahydrofuran and 1 ,4-dioxane.
  • suitable noncyclic acetals are, for example, dimethoxymethane, dieth- oxymethane, 1 ,1 -dimethoxyethane and 1 ,1 -diethoxyethane.
  • Suitable cyclic acetals are 1 ,3-dioxane and especially 1 ,3-dioxolane.
  • suitable noncyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
  • Suitable cyclic organic carbonates are compounds of the general formulae (II) and (III) in which R 1 , R 2 and R 3 may be the same or different and are selected from hydrogen and Ci-C4-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- butyl and tert-butyl, where R 2 and R 3 are preferably 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.
  • Another preferred cyclic organic carbonate is vinylene carbonate, formula (IV).
  • the solvent(s) is (are) preferably used in what is known as the anhydrous state, i.e. with a water content in the range from 1 ppm to 0.1 % by weight, determinable, for example, by Karl Fischer titration.
  • inventive electrochemical cells comprise one or more conductive salts, preference being given to lithium salts.
  • suit- able lithium salts are LiPF 6 , LiBF 4 , LiCI0 4 , LiAsF 6 , LiCF 3 S0 3 , LiC(CnF 2n+ iS02)3, lithium imides such as LiN(C n F2n+iS02)2, where n is an integer in the range from 1 to 20,
  • LiN(S0 2 F) 2 Li 2 SiF 6 , LiSbF 6 , LiAICU, and salts of the general formula (C n F 2 n + iS02)mXLi, where m is defined as follows:
  • m 3 when X is selected from carbon and silicon.
  • inventive electrochemical cells comprise one or more separators by which the electrodes are mechanically separated.
  • Suitable separators are polymer films, especially porous polymer films, which are unreactive toward metallic lithium and toward lithium sulfides and lithium polysulfides.
  • Particularly suitable materials for separators are polyolefins, especially porous polyethylene in film form and porous polypropylene in film form.
  • Separators made from polyolefin especially made from polyethylene or polypropylene, may have a porosity in the range from 35 to 45%. Suitable pore diameters are, for example, in the range from 30 to 500 nm.
  • the separators selected may be separators made from PET nonwovens filled with inorganic particles.
  • Such separators may have a porosity in the range from 40 to 55%. Suitable pore diameters are, for example, in the range from 80 to 750 nm.
  • Inventive electrical cells are notable for particularly high capacitances, high performance even after repeated charging, and significantly delayed cell death. Shuttling can be suppressed very efficiently. Inventive electrical cells are very suitable for use in automobiles, aircraft, ships or stationary energy stores. Such uses form a further part of the subject matter of the present invention.
  • the present invention further provides a process for producing inventive composite materials, which is also referred to as inventive production process in the context of the present invention.
  • inventive production process the procedure may be, for example, that
  • organic polymer (A), sulfur (B) and carbon (C) are each as defined above.
  • Organic polymer (A) is preferably selected from polyethylene, polypropylene, polyacry- lonitrile, polybutadiene, polystyrene and copolymers of at least two comonomers se- lected from ethylene, propylene, styrene, acrylonitrile and 1 ,3-butadiene, most preferably from acrylonitrile.
  • the inventive production process can be performed in the presence of a solvent, for example toluene or ethanol. However, preference is given to performing the inventive production process without solvent. In one embodiment of the present invention, the inventive production process is performed at ambient pressure, i.e. at standard pressure.
  • the inventive production process is performed at elevated pressure, for example at 1 .1 to 100 bar.
  • the inventive production process is performed at autogenous pressure.
  • any pressure for example 10 bar or else standard pressure
  • the reaction is performed in a pressure vessel, for example an autoclave.
  • Gaseous by-products which form, es- pecially hbS, can increase the pressure during the reaction, for example to pressures of up to 100 bar or else more.
  • the pressure measurement can be used to monitor the reaction.
  • the inventive production process can be performed over a period in the range from 10 minutes up to 100 hours, preference being given to two to 24 hours.
  • the reaction it is preferred, after the reaction has ended, to free the inventive composite material obtained of hbS, for example to degas it.
  • the degassing can be accomplished, for example, by evacuating or by purging with an inert gas, for example with nitrogen or with a noble gas such as argon.
  • Inventive composite material is obtained, generally in powder form.
  • the present invention further provides a process for operating automobiles, aircraft, ships or stationary energy stores using at least one inventive electrical cell.
  • EPMA electron probe microanalysis
  • EDXS Energy Dispersive X-Ray Spectroscopy
  • the sample of inventive composite material CM.2 comprised particles which comprised reaction product of polyacrylonitrile with sulfur and carbon black and which had a mean diameter in the range from 5 to 50 ⁇ .
  • Anode Li foil, thickness 50 ⁇ ,
  • Electrolyte 8% by weight of LiN(S0 2 CF 3 ) 2 , 46% by weight of 1 ,3-dioxolane and 46% by weight of 1 ,2-dimethoxyethane.
  • the charging and discharging of the cell was carried out with a current of 4.19 mA at potentials in the range of 1 .8 - 2.5.
  • the cell capacitance was 41 .2 mA-h. Results are summarized in table 1 .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne des matériaux composites, leur fabrication et leur utilisation dans des piles voltaïques. L'invention concerne, plus précisément, un matériau composite comprenant le produit réactionnel (A) d'au moins un polymère organique, (B) du soufre et (C) du carbone dans un polymorphe comprenant au moins 60 % d'atomes de carbone à hybridation sp2 et, en outre, des particules ou des domaines comprenant du carbone (C) rempli de soufre (B).
EP11786222.7A 2010-05-28 2011-05-30 Matériaux composites, leur fabrication et leur utilisation dans des piles voltaïques Withdrawn EP2576682A4 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11786222.7A EP2576682A4 (fr) 2010-05-28 2011-05-30 Matériaux composites, leur fabrication et leur utilisation dans des piles voltaïques

Applications Claiming Priority (3)

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EP11786222.7A EP2576682A4 (fr) 2010-05-28 2011-05-30 Matériaux composites, leur fabrication et leur utilisation dans des piles voltaïques
PCT/IB2011/052353 WO2011148357A1 (fr) 2010-05-28 2011-05-30 Matériaux composites, leur fabrication et leur utilisation dans des piles voltaïques

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Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011002720A1 (de) * 2011-01-14 2012-07-19 Robert Bosch Gmbh Kathodenzusammensetzung
JP5692703B2 (ja) * 2011-03-28 2015-04-01 国立大学法人東京農工大学 リチウム硫黄電池用正極材料、リチウム硫黄電池、及び、リチウム硫黄電池用正極材料の製造方法
DE102011075051A1 (de) * 2011-05-02 2012-11-08 Robert Bosch Gmbh Kathodenmaterial für Alkali-Schwefel-Zelle
US9099223B2 (en) 2011-05-27 2015-08-04 Basf Se Composite materials, production thereof and use thereof in electrical cells
WO2012164443A1 (fr) * 2011-05-27 2012-12-06 Basf Se Matériaux composites, leur production et leur utilisation dans des cellules électriques
JP2015515099A (ja) 2012-03-27 2015-05-21 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ ナトリウム−酸素電池
DE102012209635A1 (de) * 2012-06-08 2013-12-12 Robert Bosch Gmbh Verfahren zum Herstellen eines Polyacrylnitril-Schwefel-Kompositwerkstoffs
CN103531748B (zh) * 2012-07-06 2015-09-30 清华大学 锂离子电池电极活性物质的制备方法
JP6115914B2 (ja) * 2013-03-13 2017-04-19 国立研究開発法人産業技術総合研究所 硫黄変性ニトリル基含有共重合体樹脂及びその用途
CN104577050B (zh) * 2013-10-17 2017-07-07 清华大学 锂离子电池电极活性物质及其制备方法
KR101575439B1 (ko) * 2013-12-27 2015-12-07 현대자동차주식회사 이종바인더가 적용된 리튬황 전지의 유황 양극
US10665895B2 (en) 2014-04-18 2020-05-26 Seeo, Inc. Polymer composition with olefinic groups for stabilization of lithium sulfur batteries
CN106463704B (zh) * 2014-04-18 2019-10-11 西奥公司 长循环寿命的锂硫固态电化学电池
WO2016019544A1 (fr) * 2014-08-07 2016-02-11 Robert Bosch Gmbh Composite polyacrylonitrile-soufre, sa préparation et son utilisation
EP3116052A1 (fr) 2015-07-08 2017-01-11 Basf Se Cellules métal-oxygène rechargeables
JP6731663B2 (ja) * 2015-09-02 2020-07-29 住友ゴム工業株式会社 硫黄系正極活物質、正極およびリチウムイオン二次電池
US20190181425A1 (en) * 2016-08-31 2019-06-13 William Marsh Rice University Anodes, cathodes, and separators for batteries and methods to make and use same
US11984576B1 (en) 2019-10-01 2024-05-14 William Marsh Rice University Alkali-metal anode with alloy coating applied by friction
CN112803003B (zh) * 2021-01-26 2021-08-17 浙江大学 一种具有高循环稳定性与高库伦效率的锂硫二次电池
EP4283694A1 (fr) * 2022-05-24 2023-11-29 Universität Stuttgart Matériaux de cathode pour batteries au lithium-soufre

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1214074C (zh) * 2002-04-17 2005-08-10 中国科学院上海微系统与信息技术研究所 电化学电源正极用单质硫/导电聚合物复合材料及方法
KR100467455B1 (ko) * 2002-07-10 2005-01-24 삼성에스디아이 주식회사 리튬 황 전지용 양극 활물질 조성물 및 이를 사용하여 제조된 리튬 황 전지
JP4456448B2 (ja) * 2004-09-22 2010-04-28 アオイ電子株式会社 硫黄および／またはｓ−ｓ結合を有する硫黄化合物を含む電池正極材料及びその製造方法
US7745528B2 (en) * 2006-10-06 2010-06-29 The Trustees Of Princeton University Functional graphene-rubber nanocomposites
US20110186789A1 (en) * 2008-05-22 2011-08-04 The University Of North Carolina At Chapel Hill Synthesis of graphene sheets and nanoparticle composites comprising same
JP5534227B2 (ja) * 2008-10-17 2014-06-25 独立行政法人産業技術総合研究所 硫黄変性ポリアクリロニトリル、その製造方法、及びその用途
JP5358792B2 (ja) * 2008-12-26 2013-12-04 独立行政法人産業技術総合研究所 硫黄変性ポリアクリロニトリルシート、その製造方法及びその用途
CN101577323B (zh) * 2009-06-11 2011-08-31 上海交通大学 一种二次锂硫电池硫基正极及其制备方法
JP5233891B2 (ja) * 2009-07-23 2013-07-10 株式会社豊田中央研究所 蓄電デバイス及び電極活物質の製造方法
JPWO2011129103A1 (ja) * 2010-04-16 2013-07-11 株式会社豊田自動織機 リチウムイオン二次電池用正極及びその正極を有するリチウムイオン二次電池

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CN102906177A (zh) 2013-01-30
EP2576682A4 (fr) 2015-10-28
JP2013533904A (ja) 2013-08-29
CN102906177B (zh) 2014-12-10
KR20130113346A (ko) 2013-10-15
WO2011148357A1 (fr) 2011-12-01

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