EP2885831A2 - Matériaux composites pour batteries lithium-soufre - Google Patents

Matériaux composites pour batteries lithium-soufre

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Publication number
EP2885831A2
EP2885831A2 EP13829434.3A EP13829434A EP2885831A2 EP 2885831 A2 EP2885831 A2 EP 2885831A2 EP 13829434 A EP13829434 A EP 13829434A EP 2885831 A2 EP2885831 A2 EP 2885831A2
Authority
EP
European Patent Office
Prior art keywords
sulfur
carbon composite
composite material
particles
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Withdrawn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
EP13829434.3A
Other languages
German (de)
English (en)
Other versions
EP2885831A4 (fr
Inventor
Alexander Panchenko
Evgueni Klimov
Oliver Gronwald
Klaus Leitner
Peter Przybylski
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 EP13829434.3A priority Critical patent/EP2885831A4/fr
Publication of EP2885831A2 publication Critical patent/EP2885831A2/fr
Publication of EP2885831A4 publication Critical patent/EP2885831A4/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Withdrawn legal-status Critical Current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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • 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
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • 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
    • 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
    • H01M4/626—Metals
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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 sulfur-carbon composite materials comprising at least one carbon composite material
  • the present invention also relates to a process for the preparation of sulfur-carbon composite materials according to the invention, cathode materials for electrochemical cells comprising sulfur-carbon composite materials according to the invention, corresponding electrochemical cells and the use of carbon composite materials for the production of electrochemical cells.
  • Saving energy has long been an object of growing interest.
  • Electrochemical cells such as batteries or accumulators, can be used to store electrical energy. Of particular interest since recently the so-called lithium-ion batteries. They 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 with the formation of sulfur-sulfur bonds
  • Cathode which macroscopically corresponds to an expansion or shrinkage, that is a volume change, the cathode.
  • the cathode in a lithium sulfur cell usually contains carbon black or carbon black mixtures as conductive additives and binders.
  • the binders usually 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 for the connection of the sulfur-soot mixture on the dissipation materials of the cathode, such as metal foils, metal nets or metal-coated plastic films.
  • WO 2009/054987 describes polyvinyl alcohol as a primer layer on an aluminum layer, the aluminum layer serving as a Abieiter, also called a current collector, for a sulfur cathode.
  • each polyvinyl alcohol is used as a binder by sulfur and soot particles are combined with polyvinyl alcohol.
  • 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, a good adhesion of the cathode materials on the dissipation materials, a high electrical conductivity of the cathode materials, an increase in the cathode capacity, an increase in the life of the electrochemical cell, improved mechanical stability of the cathode or a reduced volume change of the cathode during a charging 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.
  • cathode material for a lithium-sulfur cell, which has advantages over one or more properties of a known cathode material advantages, in particular a cathode material, the construction of cathodes with improved electrical conductivity associated with high cathode capacity , with high mechanical stability and long life allowed.
  • the sulfur-carbon 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.
  • the sulfur-carbon composite materials of the present invention are particulate composites, particularly fiber composites.
  • the sulfur-carbon composite material according to the invention contains as component (A) at least one carbon composite material, also referred to below as carbon composite (A), which as component (a) is a charring product of at least one carbonaceous starting material, also referred to below as charring product (a), and therein including as component (aa) particles of at least one electrically conductive additive, hereinafter also referred to as particles (aa) for short, wherein the particles (aa) have an aspect ratio of at least 10.
  • the sulfur-carbon composite material according to the invention as component (B) contains elemental sulfur, hereinafter also called sulfur (B).
  • the carbon product (a) contained in the carbon composite (A), which is a solid, can be prepared from various carbonaceous raw materials. Both the production processes of charring products and the suitable carbonaceous starting materials which can be used in the production process are known in principle to the person skilled in the art. Carbonates are usually formed as solid, carbon-rich residues in the pyrolysis of carbonaceous feedstocks with heat input and complete or at least substantially complete oxygen exclusion to prevent oxidation of the carbon from the carbonaceous feedstock to carbon monoxide or carbon dioxide as much as possible.
  • charring products from pyrolysis processes are, for example, charcoal, animal charcoal, coke of brown or hard coal or carbon fibers of polyacrylonitrile.
  • the char product (a) may also be referred to as the carbon matrix obtainable by pyrolysis of a carbonaceous feedstock.
  • carbonaceous starting material is selected from carbohydrates, resins, coke, pitch, polyacrylonitrile, styrene-acrylonitrile copolymers, melamine-formaldehyde resins and phenol-formaldehyde resins.
  • Particularly preferred carbonaceous starting materials are carbohydrates, such as, for example, mono-, di- or polysaccharides, in which formally only carbon remains behind due to elimination of water.
  • the carbohydrate is starch.
  • the sulfur-carbon composite material according to the invention is characterized in that the carbon-containing starting material terial is selected from carbohydrates, resins, coke, pitch, polyacrylonitrile, styrene-acrylonitrile copolymers, melamine-formaldehyde resins and phenol-formaldehyde resins, in particular from carbohydrates.
  • the carbon content of the carbonization product (a) is preferably more than 80% by weight, more preferably more than 90% by weight, in particular more than 95% by weight to not more than 100% by weight, based on the mass of the char (a) determined by elemental analysis.
  • the particles (aa) contained in the carbon composite (A) have an aspect ratio of at least 10, preferably at least 20, particularly preferably at least 40, in particular at least 80.
  • the aspect ratio of a particle is understood to mean the ratio of the length of the particle to the thickness of the particle. Accordingly, particles with an aspect ratio of at least 10 may be fibrous or platelet-shaped.
  • the particles (aa) of at least one electrically conductive additive are preferably fiber-shaped, the thickness of a fiber being designated better than its diameter.
  • the length and the diameter of the particles, in particular of the fibers are determined by means of scanning electron micrographs or light microscopic images. From the values thus determined, the aspect ratio is calculated.
  • the thickness or the mean diameter of the particles of the electrically conductive additive can in principle be varied within a wide range.
  • the particles of the electrically conductive additive preferably have a thickness or in particular an average diameter in the range from 50 nm to 100 ⁇ m, particularly preferably in the range from 60 nm to 1000 nm, in particular in the range from 70 nm to 200 nm.
  • the mean diameter of the particles is determined as described above with the aid of scanning electron micrographs or light microscopic images.
  • the sulfur-carbon composite material according to the invention is characterized in that the particles of the electrically conductive additive have an average diameter of 50 nm to 100 ⁇ m.
  • the particles of the electrically conductive additive preferably have an electrical conductivity in the range from 0.1 mS / cm to 30,000 S / cm, more preferably in the range from 100 mS / cm to 30,000 mS / cm.
  • the sulfur-carbon composite material according to the invention is characterized in that the particles of the electrically conductive additive have an electrical conductivity of from 0.1 mS / cm to 30 000 S / cm.
  • Suitable particles of an electrically conductive additive are known in principle to the person skilled in the art.
  • the particles of the electrically conductive additive are preferably selected from carbon fibers, fibers from transparent metal oxides selected from indium-tin oxide, Al-doped zinc oxide, Ga-doped zinc oxide, In-doped zinc oxide, F-doped tin dioxide, Sb-doped Tin dioxide, fibers of metal carbides selected from WC, MoC and TiC, as well as metal fibers selected from aluminum and steel.
  • the particles of the electrically conductive additive are carbon fibers.
  • Methods for producing particles of an electrically conductive additive, in particular of fibers of an electrically conductive additive are known in principle to the person skilled in the art.
  • carbon fibers can be obtained by pyrolysis of polyacrylonitrile fibers.
  • Commercially available are carbon fibers from a number of suppliers.
  • Fibers of transparent metal oxides such as, for example, Al-doped zinc oxide or Sb-doped tin dioxide, can be produced, for example, by means of electrospinning and subsequent calcination, as described in WO2010 / 122049 or WO201 1/054701.
  • the sulfur-carbon composite material according to the invention is characterized in that the particles of the electrically conductive additive are selected from carbon fibers, fibers of transparent metal oxides selected from indium-tin-oxide, Al-doped zinc oxide, Ga-doped zinc oxide, In-doped zinc oxide, F-doped tin dioxide, Sb-doped tin dioxide, metal carbide fibers selected from WC, MoC and TiC, and metal fibers selected from aluminum and steel.
  • the proportion by weight of the particles of the electrically conductive additive relative to the total weight of the carbon composite material (A) can be varied within a wide range.
  • the proportion by weight of the particles of the electrically conductive additive based on the total weight of the carbon composite material (A) is preferably in the range from 0.1 to 60% by weight, more preferably in the range from 1 to 40% by weight, in particular in the range from 5 to 25% by weight.
  • the sulfur-carbon composite material according to the invention is characterized in that the weight fraction of the particles of the electrically conductive additive based on the total weight of the carbon composite material (A) is in the range of 0.1 to 60 wt .-%.
  • the sum of the weight fractions of char product (a) and of particles of the electrically conductive additive (aa) in the carbon composite (A) is at least 80% by weight, particularly preferably at least 90% by weight, in particular at least 95 wt .-% to at most nearly 100 wt .-%.
  • the proportions by weight can be determined by elemental analysis, taking into account the chemical composition of the starting components.
  • the carbon composite material (A) comprises a char product (a) which is the char product of a polysaccharide, particularly starch, and includes particles (aa) of at least one electrically conductive additive which are carbon fibers having a mean diameter in the range of 70 nm to 200 nm and an aspect ratio of at least 10, with particular preference being given to the sum of the weight fractions of char (a) and the carbon fibers used as particles (aa) in the range from 95% by weight to 100% by weight. % lies.
  • the carbon content of the carbon composite (A) is preferably more than 80 wt .-%, more preferably more than 90 wt .-%, in particular more than 95 wt .-% to at most nearly 100 wt .-% based on the mass of the carbon composite (A) determined by elemental analysis.
  • the sulfur-carbon composite material according to the invention contains elemental sulfur as component (B), elementary sulfur being known as such.
  • the sulfur in the carbon composite (A) is finely and homogeneously distributed.
  • the average particle size of the sulfur is in the range of 0.1 to 50 ⁇ , preferably in
  • the mean particle size of the sulfur in the sulfur-carbon composite material can be determined by means of scanning electron micrographs.
  • the proportion by weight of sulfur based on the sum of the weight proportions of the carbon composite material (A) and the sulfur (B) can be varied within a wide range.
  • the weight fraction of sulfur based on the sum of the weight proportions of the carbon composite material and the sulfur in the range of 10 to 95 wt .-%, particularly preferably in the range of 30 to 90 wt .-%, in particular in the range of 50 to 85 wt. -% determined by elemental analysis.
  • the sulfur-carbon composite material according to the invention is characterized in that the weight fraction of sulfur based on the sum of the weight proportions of the carbon composite material and the sulfur is in the range of 10 to 95 wt .-%.
  • the carbon composite (A) or the sulfur-carbon composite material according to the invention can be produced in different forms depending on the particular production process. Depending on the dimensions of the reactor used, it is possible in principle to produce moldings having spatial dimensions in the range from 0.001 m to 1 m, that is to say moldings having volumes in the range from 10 -9 m 3 to 1 m 3 .
  • Mortars or grinding can be particles of the carbon composite (A) or the sulfur-Kohlenstoffkompositmaterials invention produce the average particle diameter in the range of 100 nm to 1000 ⁇ , preferably in the range of 100 ⁇ to 10 ⁇ have, more preferably at 0 , 1 to 10 ⁇
  • Such finely divided powder consisting of particulate particles are particularly preferred in the context of the present invention.
  • the sulfur-carbon composite material according to the invention is characterized in that the sulfur-carbon composite material is present in particulate form.
  • the sulfur-carbon composite material of the present invention described above can be prepared by various routes.
  • the method for producing the sulfur-carbon composite material according to the invention preferably comprises a method step in which a mixture comprising at least one carbon-containing starting material and particles of at least one electrically conductive additive, wherein the particles have an aspect ratio of at least 10, is mixed, preferably homogeneously mixed ,
  • the starting materials for the preparation of the carbon composite (A) are preferably in the form of powders, which as a rule can be mixed without difficulty. Otherwise, the mixing depending on the shape and the physical properties of the starting materials, for example, in blenders (English also called blender), mills or extruders are performed.
  • the mixing step can be carried out with or without the addition of suitable liquids, which can preferably be removed without difficulty in the subsequent carbonation step.
  • the mixture containing the carbonaceous starting material and the particles of an electrically conductive additive is converted by carbonization to the carbon composite (A), wherein a carbonization product is formed from the carbonaceous starting material.
  • the carbon composite material is mixed with elemental sulfur.
  • elemental sulfur preferably sulfur powder
  • Another object of the present invention is a process for the preparation
  • Sulfur-carbon composite material containing (A) at least one carbon composite material comprising a carbonization product of at least one carbonaceous raw material and enclosed therein
  • elemental sulfur comprising at least the process steps, (i) preparing a mixture comprising at least one carbon-containing starting material and particles of at least one electrically conductive additive, the particles having an aspect ratio of at least 10,
  • a homogeneous mixture of the starting components for the carbon composite material (A) is provided by known mixing methods with or without the addition of further excipients which can be pyrolyzed or completely removed in the carbonation step, for example water.
  • the carbon composite material (A) is prepared by carbonizing the mixture containing the carbonaceous raw material and the particles of an electrically conductive additive, wherein the carbonaceous raw material is converted into a carbonization product (a).
  • the actual carbonation step (ii) can precede one or more thermal treatment steps of the mixture of starting materials at temperatures below 200 ° C, which may be, for example, a step of adhering in the case of moistened starch or drying steps, removal of one or more solvents such as water.
  • the carbonization is carried out at a temperature in the range from 200 to 2000 ° C., preferably in the range from 300 to 1600 ° C., more preferably in the range from 400 to
  • the process according to the invention for producing a sulfur-carbon composite material is characterized in that, in process step (ii), the carbonization is carried out at at least 500 ° C., in particular in the range from 550 to 700 ° C.
  • the duration of carbonation can vary widely and, among other things, depends on the temperature at which the carbonation is carried out.
  • the carbonization time can be from 0.5 to 50 hours, preferably from 1 to 24 hours, especially from 2 to 12 hours.
  • the carbonization of the mixture comprising the carbonaceous starting material and the particles (aa) can in principle be carried out in one or more stages, for example in one or two stages.
  • a step of carbonization can be carried out in the presence or absence of oxidizing agents, for example oxygen, as long as the oxidizing agent does not completely oxidize the carbon present in the carbonaceous starting material.
  • oxidizing agents for example oxygen
  • the carbonization of the mixture comprising the carbonaceous starting material and the particles (aa) can in principle be carried out under reduced pressure, for example under reduced pressure, under normal pressure or under elevated pressure, for example in a pressure autoclave.
  • the carbonization is carried out at a pressure in the range from 0.01 to 100 bar, preferably in the range from 0.1 to 10 bar, in particular in the range from 0.5 to 5 bar or 0.7 to 2 bar.
  • the carbonation can be carried out in a closed system or in an open system in which evolved volatiles in a gas stream, inert gases or reducing gases are removed.
  • step (iii) a mixture of the carbon composite (A) and elemental sulfur (B) obtained in step (ii) is prepared.
  • a homogeneous mixture of the carbon composite material (A) with the sulfur is preferably prepared for this purpose.
  • either components (A) and (B) are comminuted separately or directly together to form a powder.
  • the mixture is preferably thermally treated. More preferably, the components (A) and (B) are heated at a temperature in the range of 100 to 200 ° C with each other.
  • Process step (iii) can be carried out both in a closed system, such as an autoclave, and in an open system, such as a piston, the material in the open system being preferably protected by superposition with a stream of an inert gas, such as argon becomes.
  • the process according to the invention for producing a sulfur-carbon composite material is characterized in that in process step (iii) in the preparation of the mixture, the carbon composite material and the elemental sulfur at a temperature in the range of 100 to 200 ° C are heated.
  • a mixture thus prepared is a composite material in which the starting materials can no longer be separated completely by manual methods.
  • the process according to the invention is suitable for producing technical sulfur-carbon composite 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 operation this means production volumes over 100 kg / day, better> 1000 kg / day, even better> 10 t / day or> 100 t / day.
  • the sulfur-carbon 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 the person 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 inventive sulfur-carbon composite material, as described above, and optionally at least one binder (C).
  • the cathode material according to the invention preferably contains at least one binder (C) in addition to the sulfur-carbon composite material according to the invention.
  • binder (C) contained in the cathode material according to the invention serves mainly for the mechanical stabilization of cathode material according to the invention.
  • binder (C) is selected from organic (co) polymers.
  • suitable organic (co) polymers may be halogenated or halogen-free. Examples are polyethylene oxide (PEO), cellulose, carboxymethylcellulose, polyvinyl alcohol, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate copolymers, styrene-butadiene copolymers, tetrafluoroethylene
  • Hexafluoropropylene copolymers vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, ethylene-chlorofluoroethylene copolymers, ethylene-acrylic acid copolymers, optionally At least partially neutralized with alkali metal salt or ammonia, ethylene-methacrylic acid copolymers, optionally at least partially neutralized with alkali metal salt or ammonia, ethylene (meth) acrylic ester copolymers, polyimides and polyisobutene.
  • PVdF-HFP vinylidene fluoride-hexafluoropropylene copolymers
  • PVdF-HFP vinyliden
  • Suitable binders are in particular polyvinyl alcohol and halogenated (co) polymers, for example polyvinyl chloride or polyvinylidene chloride, in particular fluorinated (co) polymers such as polyvinyl fluoride and in particular polyvinylidene fluoride and polytetrafluoroethylene.
  • the average molecular weight M w of binder (C) can be chosen within wide limits, suitable, for example, 20,000 g / mol to 1,000,000 g / mol.
  • the cathode material according to the invention contains in the range of 0.1 to 10 wt .-% of binder, preferably 1 to 8 wt .-% and particularly preferably 3 to 6 wt .-% based on the mass of the sulfur used according to the invention -Kohlenstoffkompositmaterials.
  • Binder (C) can be incorporated by various methods into cathode material according to the invention. For example, it is possible to dissolve soluble binders (C) such as polyvinyl alcohol in a suitable solvent or solvent mixture, for example, water / isopropanol is suitable for polyvinyl alcohol and to prepare a suspension with the other constituents of the cathode material. After application to a suitable substrate, for example an aluminum foil, the solvent or solvent mixture is removed, for example evaporated, and an electrode is obtained from the cathode material according to the invention. Suitable solvent for polyvinylidene fluoride is NMP.
  • the cathode material according to the invention may additionally contain carbon (D) which, in principle, is also the above-described carbon composite (A) which, however, has not been contacted with sulfur.
  • the additional carbon (D) is carbon in a modification comprising at least 60% sp 2 -hybridized C atoms, preferably from 75% to 100% sp 2 -hybridized C atoms.
  • This carbon is also called carbon (D) in the context of the present invention and is known as such.
  • the carbon (D) is an electrically conductive modification of carbon.
  • Carbon (D) can be selected, for example, from graphite, carbon black, carbon nanotubes, graphene or mixtures of at least two of the aforementioned substances.
  • % data refers to the total carbon (D) contained in the cathode material along with the sulfur-carbon composite material, including any impurities, and denotes percent by weight.
  • carbon (D) 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.
  • 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.
  • carbon (D) is partially oxidized carbon black.
  • carbon (D) 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 mono- xid 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 compound or carbon-containing compounds in the presence of a decomposition catalyst for example Fe, Co or preferably Ni.
  • graphene is understood as meaning almost ideal or ideally two-dimensional hexagonal carbon crystals, which are constructed analogously to individual graphite layers.
  • carbon (D) is selected from graphite, graphene, activated carbon, and especially carbon black.
  • Carbon (D) may, for example, be in the form of particles having a diameter in the range of 0.02 to 50 ⁇ m. In this case, the particle diameter means the average diameter of the secondary particles, determined as volume average by means of scanning electron micrographs.
  • carbon (D), and especially carbon black has a BET surface area in the range of 20 to 1500 m 2 / g measured according to ISO 9277.
  • cathode material in the range of 20 to 80 wt .-%, preferably 30 to 70 wt .-% of sulfur, determined by elemental analysis.
  • electrode material according to the invention contains in the range from 0.1 to 60% by weight of carbon (D), preferably from 3 to 30% by weight.
  • This carbon is also determinable, for example, by elemental analysis, where at The evaluation of the elemental analysis must take into account that carbon is also introduced via the components (A), (B) and (C) into the cathode material according to the invention.
  • Sulfur-carbon composite materials according to the invention 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 is the use of sulfur-carbon composite materials according to the invention or cathode materials according to the invention as or for the production of cathodes for electrochemical cells.
  • Sulfur-carbon composite materials according to the invention or cathode materials according to the invention are furthermore distinguished by the fact that battery cells can be produced which preferably have at least 30 cycles, more preferably at least 50 cycles, very preferably at least 100 cycles, in particular at least 200 cycles stable over at least 500 cycles.
  • Another object of the present invention are electrochemical cells containing at least one cathode, which was prepared from or using at least one sulfur-carbon composite material according to the invention or at least one cathode material according to the invention.
  • cathode that electrode is referred to as a cathode, which has a reducing effect during unloading (working).
  • sulfur-carbon composite material or cathode material according to the invention is processed into cathodes, for example in the form of endless strips, which are processed by the battery manufacturer.
  • cathodes produced from sulfur-carbon 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.
  • electrochemical cells according to the invention comprise, in addition to the sulfur-carbon composite material or cathode material according to the invention, at least one electrode containing metallic magnesium, metallic aluminum, metallic zinc, metallic sodium or preferably metallic lithium.
  • electrochemical cells according to the invention described above comprise, in addition to sulfuric acid according to the invention.
  • electrochemical cells according to the invention comprise sulfur-carbon composite material or cathode material according to the invention and another electrode, in particular an electrode containing metallic lithium, at least one nonaqueous solvent which may be liquid or solid at room temperature, is preferably liquid at room temperature, 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.
  • 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 polyalkylene glycols double capped with methyl or ethyl.
  • the molecular weight M w of suitable polyalkylene glycols and in particular 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.
  • Another preferred cyclic organic carbonate is vinylene carbonate, formula (XII).
  • the solvent or solvents are used in the so-called anhydrous state, i. with a water content in the range of 1 ppm to 0.1 wt .-%, determined for example by Karl Fischer titration.
  • electrochemical cells according to the invention comprise one or more conductive salts, preference being given to lithium salts.
  • suitable lithium salts are LiPF 6, LiBF 4, LiCI0 4, LiAsF 6, LiCF 3 S0 3, LiC (C n F 2 n + IS02) 3, lithium imides such as LiN (C n F 2n + IS02) 2, where n is an integer Number in the range of 1 to 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 conducting salts are selected from LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , LiPF 6 , LiBF 4 ,
  • LiCl 4 and particularly preferred are LiPF 6 and LiN (CF 3 SO 2) 2.
  • electrochemical cells according to the invention contain one or more separators, by means of which the electrodes are mechanically separated are.
  • 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 particularly 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. In another embodiment of the present invention, separators made from PET webs filled with inorganic particles can be used as separators. Such separators may have a porosity in the range of 40 to 55%. Suitable pore diameters are, for example, in the range from 80 to 750 nm.
  • the electrochemical cells according to the invention can be combined to give lithium-ion batteries.
  • Another object of the present invention is also the use of electrochemical cells according to the invention, as described above, in lithium-ion batteries.
  • Another object of the present invention are lithium-ion batteries, comprising at least one inventive electrochemical 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 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.
  • 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 use the same energy with electrochemical cells with lower energy density Realize runtime, so you would have to accept a higher weight for electrochemical cells.
  • Another object of the present invention is therefore the use of inventive lithium-ion batteries in devices, especially 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 those that you move yourself, such as computers, especially laptops, phones or electrical tools, for example, in the field of construction, in particular drills, cordless screwdrivers or cordless tackers.
  • Another object of the present invention is also the use of a carbon composite material comprising (a) a charring product of at least one carbonaceous starting material and enclosed therein
  • particles of at least one electrically conductive additive having an aspect ratio of at least 10, 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.
  • V-SC.2 After cooling, the resulting greyish sulfur-carbon material V-SC.2 was ground for 10 minutes at 300 rpm in a ball mill (Fritsch Pulverisette). Finally, the sulfur content in V-SC.2 was determined by elemental analysis and a value of 83% was found.
  • electrochemical cells according to FIG. 1 were constructed. In addition to those in III. the following components were used:
  • FIG. 1 shows the schematic structure of a disassembled electrochemical cell for testing composite materials according to the invention and not according to the invention.
  • the explanations in FIG. 1 mean:

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Abstract

L'invention concerne des matériaux composites à base de soufre et de carbone, contenant (A) au moins un matériau composite à base de carbone comprenant (a) un produit de carbonisation d'au moins une matière première carbonée et (aa) des particules y étant enfermées d'au moins un additif électroconducteur, les particules présentant un facteur de forme d'au moins 10, ainsi que (B) du soufre élémentaire. L'invention concerne également un procédé de fabrication des matériaux composites à base de soufre et de carbone selon l'invention, des matériaux de cathode pour cellules électrochimiques contenant des matériaux composites à base de soufre et de carbone selon l'invention, des cellules électrochimiques correspondantes et l'utilisation de matériaux composites à base de carbone pour fabriquer des cellules électrochimiques.
EP13829434.3A 2012-08-14 2013-08-05 Matériaux composites pour batteries lithium-soufre Withdrawn EP2885831A4 (fr)

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EP13829434.3A EP2885831A4 (fr) 2012-08-14 2013-08-05 Matériaux composites pour batteries lithium-soufre
PCT/IB2013/056393 WO2014027272A2 (fr) 2012-08-14 2013-08-05 Matériaux composites pour batteries lithium-soufre

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KR20150131652A (ko) * 2014-05-15 2015-11-25 현대자동차주식회사 Li2S를 이용한 복합화된 양극 구조
DE102014210249A1 (de) * 2014-05-28 2015-12-03 Volkswagen Aktiengesellschaft Verfahren zum Herstellen einer Kathode, Kathode, Lithium-Schwefel-Batterie
EP3298643B1 (fr) * 2015-05-21 2019-06-12 Basf Se Électrolytes en vitrocéramique pour batteries d'accumulateurs au lithium-soufre
JP6521545B2 (ja) * 2015-09-14 2019-05-29 エルジー・ケム・リミテッド リチウム硫黄電池用正極、その製造方法及びそれを含むリチウム硫黄電池
KR101811500B1 (ko) 2015-12-17 2017-12-22 오씨아이 주식회사 황-탄소 복합체 및 이의 제조방법
CN109565073A (zh) 2016-11-28 2019-04-02 株式会社Lg化学 包含金属硫化物纳米粒子的锂硫电池用正极活性材料及其制造方法
KR102328259B1 (ko) 2017-11-16 2021-11-18 주식회사 엘지에너지솔루션 황-탄소 복합체, 그의 제조방법 및 이를 포함하는 리튬 이차전지
KR102363968B1 (ko) 2018-02-23 2022-02-16 주식회사 엘지에너지솔루션 황-탄소 복합체, 그의 제조방법 및 이를 포함하는 리튬 이차전지
WO2019098733A1 (fr) 2017-11-16 2019-05-23 주식회사 엘지화학 Composite soufre-carbone, son procédé de préparation et batterie secondaire au lithium le comprenant
CN111095622B (zh) 2017-11-16 2023-03-31 株式会社Lg新能源 硫碳复合物、其制备方法和包含其的锂二次电池
KR102543246B1 (ko) * 2018-07-03 2023-06-14 주식회사 엘지에너지솔루션 황-탄소 복합체, 이를 포함하는 리튬-황 전지용 양극 및 리튬-황 전지
KR102733687B1 (ko) * 2018-11-28 2024-11-22 주식회사 엘지에너지솔루션 알루미늄이 도핑된 아연 산화물을 포함하는 리튬 이차전지용 양극 및 이를 구비한 리튬 이차전지

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JP2015531967A (ja) 2015-11-05
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KR20150043407A (ko) 2015-04-22
CN104541391A (zh) 2015-04-22
EP2885831A4 (fr) 2016-04-13

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