EP3645482A2 - Procédé de fabrication de fibres et de mousses contenant du carbure de silicium et utilisation de ces fibres et de ces mousses - Google Patents

Procédé de fabrication de fibres et de mousses contenant du carbure de silicium et utilisation de ces fibres et de ces mousses

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Publication number
EP3645482A2
EP3645482A2 EP18740114.6A EP18740114A EP3645482A2 EP 3645482 A2 EP3645482 A2 EP 3645482A2 EP 18740114 A EP18740114 A EP 18740114A EP 3645482 A2 EP3645482 A2 EP 3645482A2
Authority
EP
European Patent Office
Prior art keywords
silicon carbide
reactor
zone
temperature
microstructured
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Withdrawn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
EP18740114.6A
Other languages
German (de)
English (en)
Inventor
Siegmund Greulich-Weber
Rüdiger SCHLEICHER-TAPPESER
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.)
PSC Technologies GmbH
Original Assignee
PSC Technologies GmbH
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 PSC Technologies GmbH filed Critical PSC Technologies GmbH
Publication of EP3645482A2 publication Critical patent/EP3645482A2/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/956—Silicon carbide
    • C01B32/963—Preparation from compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62272—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on non-oxide ceramics
    • C04B35/62277—Fibres based on carbides
    • C04B35/62281—Fibres based on carbides based on silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62675—Thermal treatment of powders or mixtures thereof other than sintering characterised by the treatment temperature
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
    • C04B38/0029—Porous deposits from the gas phase, e.g. on a temporary support
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
    • C04B41/5057—Carbides
    • C04B41/5059—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • C23C16/325—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4486—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by producing an aerosol and subsequent evaporation of the droplets or particles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45512—Premixing before introduction in the reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/46—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for heating the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1245—Inorganic substrates other than metallic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1283—Control of temperature, e.g. gradual temperature increase, modulation of temperature
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • 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 the technical field of the production of porous materials and the accumulator technology.
  • the present invention relates to a process for the production of silicon carbide-containing fibers and silicon carbide-containing nano- and / or microstructured foams.
  • the present invention relates to silicon carbide-containing fibers and silicon carbide-containing nano- or microstructured foams and their use as sealing and insulating materials or in composite materials and their use as electrode material or for the production of electrodes.
  • the present invention relates to an apparatus for the production of silicon carbide-containing fibers and silicon carbide-containing nano- or microstructured foams. Moreover, the present invention relates to a method for applying nano- or microstructured SiliziumcarbidCumen nano- or microstructured foams, in particular for the production of electrodes having nano- or microstructured SiliziumcarbidCume, and the electrodes and accumulators obtainable by the process according to the invention containing the electrodes ,
  • the present invention relates to a device for applying fabrics with nano- and / or microstructured silicon carbide foams, in particular for the production of electrodes which have nano- or microstructured silicon carbide foams.
  • Silicon carbide with the chemical formula SiC is an extremely interesting and versatile material used in electrical engineering as well as for the production of ceramic materials. Due to its high hardness and high melting point, silicon carbide is also called carborundum and is often used as an abrasive or insulator in high-temperature reactors. In addition, silicon carbide incorporates alloys and alloys similar to a variety of elements and compounds which possess a variety of advantageous material properties, such as, for example, those of the present invention. As a high hardness, high resistance, low Weight and low sensitivity to oxidation even at high temperatures.
  • Silicon carbide-containing materials are usually prepared by sintering at high temperatures, thereby obtaining relatively porous bodies which are suitable only for a limited number of applications.
  • silicon carbide is an insulator, but due to the good thermal conductivity is suitable as a substrate for semiconductor structures, by suitable doping, in particular with the elements boron, aluminum, nitrogen and phosphorus excellent (half) conductor materials can be provided, which at temperature up to about 500 ° C can be used.
  • silicon carbide is increasingly being used as a material in the production of electrodes, particularly anodes, for lithium-ion secondary batteries.
  • anode materials for lithium-ion batteries consist of an electrical discharge plate, for example a metal foil, which is coated with graphite particles for storage of lithium ions.
  • the graphite particles are usually distributed in a binder in order to obtain a robust coating.
  • the binder is additionally mixed with soot particles.
  • the capacity of these anodes to store lithium ions is very limited. In order to increase the storage capacity of the lithium ion diode material, and thus the capacity of the battery, often at least part of the graphite is replaced by crystalline silicon or tin particles.
  • Crystalline silicon and tin particles have significantly higher storage capacities for lithium ions than graphite, but are subject to a volume change of up to 400% upon absorption and release of the lithium ions. As a result of this drastic change in volume, the binder matrix into which the silicon or tin particles are embedded is destroyed in the course of the charging and discharging cycles, so that such anodes are not cycle-tight, but their capacity decreases from cycle to cycle.
  • Silicon carbide has over the materials commonly used as material for lithium ion storage graphite, silicon and tin the advantage that it has on the one hand significantly higher lithium ion storage capacity than, for example, graphite and unlike silicon and tin undergoes no change in volume on uptake and release of lithium ions.
  • silicon carbide particles By the at least partial substitution of tin and silicon particles and also graphite by silicon carbide particles, it is possible to increase the cycle stability and the capacity of lithium ion secondary batteries.
  • silicon carbide As a material for anodes of lithium-ion batteries, the very expensive and expensive production of silicon carbide precludes a wide and standard use of silicon carbide.
  • the scientific paper describes Y. Zhao, W. Kang, L. Li, G. Yan, X. Wang, X. Zhuang, B.
  • WO 2016/078955 relates to a method for producing an electrode material for a battery electrode, in particular a lithium-ion battery, wherein the electrode material comprises a nanostructured silicon carbide, wherein silicon carbide is obtained by gasifying a Precursorgranulates and depositing on a nem substrate.
  • the rapid and complete gasification of Precursorgranulates is in this context of particular importance and can be realized in practice difficult, so that always larger amounts of undecomposed or only partially reacted precursor granules remain as waste and must be disposed of.
  • the state of the art still lacks a simple and reproducible process for producing, in particular, porous structures containing silicon carbide with high specific surface areas, which materials can be used for sealing and insulating materials or in composite materials.
  • no simple and reproducible method for producing porous silicon carbide structures has been known hitherto, which can be used as electrode materials, in particular anode materials, in lithium-ion accumulators.
  • it is usually only attempted to replace the graphite content or proportion of silicon particles or tin particles in the anode materials of lithium-ion secondary batteries with silicon carbide, which means that the anode materials furthermore have binders and conductivity improvers, such as, for example, carbon black particles Do not increase the storage capacity of the anode material.
  • a further object of the present invention is to provide an improved electrode material, in particular anode material, for lithium-ion accumulators.
  • the present invention according to a first aspect of the present invention is thus a process for the preparation of silicon carbide-containing fibers and / or silicon carbide-containing nano- or microstructured silicon carbide foams according to claim 1; Further, advantageous embodiments of this aspect of the invention are the subject of the relevant subclaims.
  • a further subject of the present invention according to a second aspect of the present invention are silicon carbide-containing fibers according to claim 15.
  • Yet another subject of the present invention according to a third aspect of the present invention is the use of silicon carbide-containing fibers according to claim 16.
  • Yet another subject of the present invention according to a fourth aspect of the present invention is the use of silicon carbide fibers for the production of anodes and / or as anode material according to claim 17.
  • silicon carbide-containing nano- and / or microstructured foams according to claim 18.
  • Another object of the present invention according to a sixth aspect of the present invention is the use of silicon carbide-containing nano- and / or microstructured foams according to claim 19.
  • Yet another subject of the present invention according to a seventh aspect of the present invention is the use of silicon carbide-containing nano- and / or microstructured SiliziumcarbidDuumen, in particular nano- and / or microstructured SiliziumcarbidCumen, for the production of anodes and / or anode materials according to claim 20.
  • subject of the present invention according to an eighth aspect of the present invention an apparatus for producing siliziumiumcarbidhal- Fibers or nano- and / or microstructured foams containing silicon carbide according to claim 21;
  • advantageous embodiments of this invention aspect are the subject of the relevant subclaims.
  • Another object of the present invention according to a ninth aspect of the present invention is a method for applying a sheet according to claim 27; Further, advantageous embodiments of this invention aspect are the subject of the relevant subclaims.
  • a further subject of the present invention according to a tenth and an eleventh aspect of the present invention is an electrode according to claim 36 or claim 37.
  • the subject matter of the present invention - according to one aspect of the present invention - is thus a process for the production of silicon carbide-containing fibers or nano- and / or microstructured foams containing silicon carbides, wherein
  • liquid and / or gaseous precursors containing at least one carbon source and at least one silicon source are introduced into a first zone, in particular a first temperature zone, of a reactor and heated to temperatures in the range of 1 .100 to 2,100 ° C, so that the precursors are decomposed, and
  • the reactor silicon carbide-containing fibers or silicon carbide-containing nano- and / or microstructured foams are deposited on a substrate.
  • the method according to the invention enables the targeted presentation of silicon carbide-containing fibers or foams based on a multiplicity of silicon carbide-containing compounds, such as, for example, silicon carbide, doped silicon carbide, non-stoichiometric silicon carbide or silicon carbide alloys.
  • silicon carbide-containing compounds such as, for example, silicon carbide, doped silicon carbide, non-stoichiometric silicon carbide or silicon carbide alloys.
  • the inventive method thus enables a particularly efficient and reproducible representation of silicon carbide-containing fibers or silicon carbide-containing nano- and / or microstructured foams at economically favorable conditions.
  • the fibers which can be obtained by the process according to the invention and nano- or microstructured foams based on optionally doped silicon carbide are outstandingly suitable as storage materials for lithium ions in lithium-ion accumulators.
  • the silicon carbide fibers or nano- and / or microstructured silicon carbide foams produced by the process according to the invention can be used either in the form of mixtures with binders as electrode material, in particular anode material, in accumulators or, in the case of nano- and / or microstructured silicon carbide foams, directly as electrodes -, In particular anode material, ie without the use of further binder.
  • the electrolytes in a lithium-ion secondary battery can completely penetrate the silicon carbide foam, so that the theoretical storage capacity of the silicon carbide is fully utilized and the lithium ions can be absorbed and released very quickly.
  • a silicon-carbide-containing fiber and / or a foam containing silicon carbide are fibers and / or foams made from compounds containing silicon carbide, ie. H. from a binary, ternary or quaternary inorganic compound whose molecular formula contains silicon and carbon.
  • a silicon carbide-containing compound does not contain any molecularly bound carbon, such as carbon monoxide or carbon dioxide; the carbon is present in a solid state structure.
  • the silicon carbide-containing compound, in particular the fibers and / or foams is usually selected from silicon carbide, non-stoichiometric silicon carbides, doped silicon carbides and silicon carbide alloys.
  • non-stoichiometric silicon carbide is to be understood as meaning a silicon carbide which does not contain carbon and silicon in a molar ratio of 1: 1 but in different proportions. Normally, a non-stoichiometric silicon carbide in the context of the present invention has a molar excess of silicon.
  • a doped silicon carbide is to be understood as meaning a silicon carbide which contains silicon and carbon either in stoichiometric or in non-stoichiometric amounts, but with small amounts of other elements, in particular from the 13th and 15th group of the Periodic Table of the Elements , in particular doped, is.
  • the electrical properties of the silicon carbides are decisively influenced by the doping of the silicon carbides, so that doped silicon carbides are particularly suitable for applications in semiconductor technology.
  • a doped silicon carbide is preferably a stoichiometric silicon carbide of the chemical formula SiC, which has at least one doping element in the parts per million (ppm) or parts per billion (ppb) range.
  • silicon carbide alloys are to be understood as meaning compounds of silicon carbide with metals, for example titanium or other compounds, such as zirconium carbide or boron nitride, which contain silicon carbide in different and strongly fluctuating proportions. Silicon carbide alloys often form high performance ceramics, which are characterized by particular hardness and temperature resistance. The inventive method is thus suitable for the production of fibers and foams from different silicon carbide-containing materials, which can be used for a variety of applications - from sealing and insulating materials on composite materials to materials for electrical and electronic applications.
  • a precursor is to be understood as meaning, in particular, a chemical compound or a mixture of chemical compounds which reacts by chemical reaction and / or under the action of energy, in particular heat, to one or more target compounds.
  • a precursor may also be a solution or dispersion of chemical compounds which react under process conditions to give the target compounds; This special embodiment of the precursor is also referred to below as precursor sol.
  • a silicon source or a carbon source are compounds which can release silicon or carbon under process conditions such that silicon carbide or, in the presence of doping and / or alloying reagents or elements, a doped silicon carbide or a silicon carbide alloy is formed.
  • silicon and carbon do not have to be released in elemental form, but it is sufficient if the liberated reactive compounds under process conditions to silicon carbide or Siliziumcarbidlegie- ments react.
  • the silicon source, the carbon source and, if appropriate, the doping and / or alloying reagents may be either directly gaseous or liquid precursor compounds or else their reaction products, if the precursor is in the form of a precursor sol, for example.
  • liquid and / or gaseous precursors are to be understood as meaning that they are liquid and / or gaseous before being introduced into the reactor, where they pass into the gas phase as directly as possible after introduction into the reactor, where they decompose and release reactive species to the corresponding silicon carbide-containing materials or fibers and foams, respectively.
  • a substrate is to be understood as the surface on which the silicon carbide-containing fibers or the silicon carbide-containing nano- and / or microstructured foams are deposited.
  • a substrate in the context of the present invention is to be understood as meaning both a pure separation surface for fibers and foams, which are subsequently removed again from the surface, and a material to be coated.
  • silicon carbide-containing fibers or foams with crosslinked silicon carbide-containing fibers are produced.
  • silicon-carbide-containing nano- and / or microstructured foams are to be understood as meaning, in particular, three-dimensional, highly porous network structures made of silicon carbide-containing fibers.
  • the silicon carbide-containing nano- and / or microstructured foams are thus porous open-cell foams, which are highly permeable in particular for liquids and thus can be used in an outstanding manner as electrode material for accumulators.
  • the silicon carbide-containing foams can also be used as sealing and insulating materials, for example for damping or absorbing vibration and sound.
  • the silicon carbide-containing nano- and / or microstructured foams are composed of interconnected, in particular crosslinked, silicon carbide-containing fibers, preferably three-dimensional networks of silicon carbide-containing fibers.
  • Nanostructured is to be understood as meaning that pores are created in the three-dimensional structure with dimensions in the nanometer range by the individual fibers containing silicon carbide.
  • microstructured is to be understood as meaning that the silicon-carbide-containing fibers create pores in the silicon carbide-containing structure whose extent lies in the micrometer range.
  • the silicon carbide-containing nano- and / or microstructured foams having a layer thickness of 0.5 ⁇ to 15 mm, in particular 0.8 ⁇ to 12 mm, preferably 1 ⁇ to 10 mm, on the Substrate are deposited.
  • Silicon carbide foams with the aforementioned thicknesses are outstandingly suitable as anode material for Lithium ion accumulators and in particular have very good lithium ion storage capacities, while foams based on silicon carbide alloys or non-stoichiometric silicon carbides can be used particularly well for insulating and sealing purposes or for suspensions.
  • the silicon carbide-containing fibers of the silicon carbide-containing nano- and / or microstructured foams have an aspect ratio of greater than 3, in particular greater than 10, preferably greater than 100.
  • the silicon carbide-containing fibers of the silicon carbide-containing nano- and / or microstructured foams diameter in the range of 5 nm to 5 ⁇ , in particular 10 nm to 2 ⁇ have.
  • the silicon carbide-containing fibers of the silicon carbide-containing nano- and / or microstructured foams have lengths in the range of 5 nm to 10 ⁇ m, in particular 5 nm to 1 ⁇ m, preferably 5 nm to 500 ⁇ m.
  • the fibers containing silicon carbide have an aspect ratio of greater than 3, in particular greater than 10, preferably greater than 100.
  • the silicon carbide-containing fibers diameter in the range of 5 nm to 5 ⁇ , in particular 10 nm to 2 ⁇ have.
  • the silicon carbide-containing fibers have lengths in the range of 100 nm to 30 mm, in particular 500 nm to 10 mm, preferably 1 ⁇ m to 5 mm.
  • the silicon carbide-containing fibers and the silicon carbide-containing nano and / or microstructured foams from optionally doped nanocrystalline or monocrystalline, in particular nanocrystalline, silicon carbide.
  • the outstanding electrical properties of silicon carbide, in particular doped silicon carbide, are only relevant if the silicon carbide is present in crystalline form, in particular in monocrystalline or at least nanocrystalline form.
  • the silicon carbide is preferably present in the silicon carbide fibers and the silicon carbide foams as cubic polytype 3C-SiC or in the form of the hexagonal polytype 4H-SiC and 6H-SiC.
  • Silicon carbide-containing materials of optionally doped nanocrystalline or monocrystalline silicon carbide are particularly suitable for use in electrical engineering, in particular for example in batteries.
  • the silicon carbide-containing fibers and the silicon carbide-containing nano- and microstructured foams consist of nanocrystalline or monocrystalline, in particular nanocrystalline, non-stoichiometric silicon carbide or nanocrystalline or monocrystalline, in particular nanocrystalline, silicon carbide alloys.
  • Non-stoichiometric silicon carbides and silicon carbide alloys are suitable for the production of particularly durable and resistant materials which can withstand even extreme stresses due to high temperatures, chemicals and mechanical stress.
  • the silicon carbide can be doped.
  • the silicon carbide is doped with an element selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, boron, aluminum, gallium, indium and mixtures thereof.
  • the silicon carbide is doped in the context of the present invention, it has proven useful if the doped silicon carbide contains the doping element in amounts of from 0.000001 to 0.0005% by weight, in particular 0.000001 to 0.0001% by weight. , preferably 0.000005 to 0.0001 wt .-%, preferably 0.000005 to 0.00005 wt .-%, based on the doped silicon carbide containing. For the targeted adjustment of the electrical properties of silicon carbide thus exceed extremely small amounts of doping elements completely.
  • the non-stoichiometric silicon carbide is usually a silicon carbide of the general formula (I)
  • x 0.05 to 0.8, in particular 0.07 to 0.5, preferably 0.09 to 0.4, preferably 0.1 to 0.3.
  • Such silicon-rich silicon carbides have a particularly high mechanical strength and are suitable for a variety of applications as ceramics, in particular as a reinforcing filler in composite materials.
  • non-stoichiometric silicon carbide is doped, in particular with the abovementioned elements.
  • the silicon carbide alloy is usually selected from MAX phases, alloys of silicon carbide with elements, in particular metals, and Alloys of silicon carbide with metal carbides and / or metal nitrides.
  • Such silicon carbide alloys contain silicon carbide in varying and strongly fluctuating proportions.
  • silicon carbide is the main constituent of the alloys.
  • the silicon carbide alloy contains silicon carbide only in small amounts.
  • the silicon carbide alloy comprises the silicon carbide in amounts of from 10 to 95% by weight, in particular from 15 to 90% by weight, preferably from 20 to 80% by weight, based on the silicon carbide alloy.
  • M stands for an early transition metal from the third to sixth group of the Periodic Table of the Elements, while A stands for an element of the 13th to 16th group of the periodic table of the elements.
  • X is either carbon or nitrogen.
  • MAX phases are of interest whose molecular formula contains silicon carbide (SiC), ie silicon and carbon.
  • MAX phases often have unusual combinations of chemical, physical, electrical, and mechanical properties, as they exhibit both metallic and ceramic behavior, depending on conditions. This includes, for example, a high electrical and thermal conductivity, high resilience to thermal shock, very high hardnesses and low thermal expansion coefficients.
  • the silicon carbide alloy is a MAX phase
  • the MAX phase is selected from Ti 4 SiC 3 and Ti 3 SiC.
  • the abovementioned MAX phases are highly resistant to chemicals as well as to oxidation at high temperatures, in addition to the properties already described.
  • the material containing silicon carbide and / or the silicon carbide-containing nano- or microstructured foams is an alloy of silicon carbide, then it has proven useful if the alloy is selected from alloys of silicon carbide with metals from the group of Al, Ti, V, Cr, Mn, Co, Ni, Zn, Zr and mixtures thereof.
  • the alloy of silicon carbide is selected from alloys of silicon carbide with metal carbides and / or nitrides, it has proven useful if the alloys of silicon carbide with metal carbides and / or nitrides are selected from the group of boron carbides, in particular B 4 C, chromium carbides, in particular Cr 2 C3, titanium carbides, in particular TiC, molybdenum carbides, in particular Mo 2 C, niobium carbides, in particular NbC, tantalum carbides, in particular TaC, vanadium carbides, in particular VC, zirconium carbides, in particular ZrC, tungsten carbides, in particular WC, boron nitride, in particular BN, and mixtures thereof.
  • boron carbides in particular B 4 C
  • chromium carbides in particular Cr 2 C3
  • titanium carbides in particular TiC
  • molybdenum carbides in particular Mo 2 C
  • niobium carbides in particular NbC
  • the temperature in the first Zone of the reactor in the range of 1 .200 to 2,000 ° C, in particular 1 .300 to 1,900 ° C, is set.
  • the temperature in the second zone of the reactor is lower than in the first zone of the reactor.
  • the first zone, in particular the first temperature zone, of the reactor usually begins in the region in which the gaseous or liquid precursors are introduced into the reactor and occupies at least half of the reactor volume. In this area, the precursors are decomposed into reactive species which then enter the second zone, in particular the second temperature zone, in which a somewhat lower temperature usually prevails, so that first condensates of the reactive species are formed.
  • the deposition of the silicon carbide-containing material, in particular in the form of foams or separate fibers then takes place on the substrate.
  • the temperature of the substrate is again lowered relative to the temperature in the second zone, in particular the second temperature zone of the reactor. This ensures in particular that the fibers or foams containing silicon carbide are formed exclusively on the substrate and do not precipitate at other points of the reactor, for example the reactor walls.
  • the temperature in the second zone of the reactor is set at least 30 ° C., in particular at least 40 ° C., preferably at least 50 ° C., lower than in the first zone of the reactor.
  • the temperature in the second zone of the reactor at most 300 ° C, in particular at most 250 ° C, preferably at most 200 ° C, is set lower than in the first zone of the reactor.
  • the temperature in the second zone of the reactor is from 30 to 300 ° C, in particular 40 to 250 ° C, preferably 50 to 200 ° C, is set lower than in the first zone of the reactor.
  • the temperature in the second zone of the reactor in the range of 1 .000 to 2,000 ° C, in particular 1 .050 to 1,900 ° C, preferably 1 .100 to 1. 800 ° C, is set.
  • the heating of the precursors in the first zone can be done in a variety of ways. However, it has proven useful if the precursors are heated by electromagnetic radiation, in particular infrared radiation and / or microwave radiation, and / or electrical resistance heating. Particularly good results are obtained in this context when the precursors are heated by microwave radiation and / or electrical resistance heating.
  • the precursors are selected from mixtures of liquid and / or gaseous carbon and silicon sources and solutions containing carbon and silicon sources or dispersions, in particular SiC precursor sols, and mixtures thereof.
  • liquid and / or gaseous carbon sources are used as precursor in the context of the present invention, it may be provided that the liquid and / or gaseous carbon source is selected from alkanes, amines, alkyl halides, aldehydes, ketones, carboxylic acids, amides, Carboxylic esters and mixtures thereof, in particular C to Cs alkanes, C to C 4 alkyl primary and secondary, Cr to Cs alkyl halides, Cr to Cs aldehydes, Cr to C 8 ketones, Cr to C 8 carboxylic acids, Cr to C 8 - Amides, C 1 to C 8 - carboxylic acid esters and mixtures thereof.
  • the gaseous and / or liquid carbon source is selected from C 1 to C 5 alkanes, in particular C 4 to C 4 alkanes, and mixtures thereof.
  • the gaseous or liquid carbon source is a short-chain and thus readily volatile alkane.
  • liquid and / or gaseous silicon source is selected from silanes, siloxanes and mixtures thereof, preferably silanes.
  • siloxanes are used as precursors in the context of the present invention, it is possible, when suitable siloxanes are selected, for the siloxane or siloxanes to be both the carbon source and the silicon source and no further precursors to be used, with the exception of possible doping reagents have to.
  • siloxane is used as the liquid and / or gaseous silicon source in the context of the present invention, it has proven useful if the siloxane is selected from alkyl and phenyl siloxanes, in particular methyl and phenyl siloxanes.
  • the siloxane has a weight average molecular weight in the range of 500 to 5,000 g / mol, in particular 750 to 4,000 g / mol, preferably 1,000 to 2,000 g / mol.
  • the silicon source is a silane.
  • Silanes are often highly volatile compounds, which rapidly convert into the gas phase and react without leaving any residue or can easily be decomposed. Particularly good results are obtained in the context of the present invention, when the silane is selected from monosilane (SiH 4 ), halosilanes, alkylsilanes, alkoxysilanes and mixtures thereof.
  • R 1 , R 2 alkyl, especially C 1 to C 8 alkyl, preferably C 1 to C 3 alkyl, preferably C and / or C 2 alkyl;
  • Aryl in particular C 6 - to C 2 o-aryl, preferably C 6 - to C 5 -aryl, preferably C 6 - to C -o-aryl;
  • Olefin in particular terminal olefin, preferably C 2 - to Cio-olefin, preferably C 2 - to C 8 -olefin, more preferably C 2 - to C 5 -olefin, very particularly preferably C 2 - and / or C 3 -olefin, particularly preferably vinyl;
  • Halide especially chloride and / or bromide
  • Alkoxy in particular C to C6-alkoxy, more preferably Cr to
  • the silane is selected from SiH 4 , SiCl 4 , Si (CH 3 ) 4 , Si (OCH 3 ) 4 , Si (OCH 2 CH 3 ) 4, and mixtures thereof.
  • the precursors in particular the mixture of gaseous and / or liquid carbon and silicon sources, furthermore have at least one doping reagent.
  • doping reagents in particular liquid and / or gaseous doping reagents are advantageous, in particular compounds of the elements of the 13th and 15th group of the Periodic Table of the Elements can be used as doping reagents.
  • the doping reagent is a liquid or gaseous compound of an element selected from the group consisting of boron, aluminum, gallium, indium, nitrogen, phosphorus, arsenic, antimony, bismuth and ren mixtures.
  • the hydrides, ie hydrogen compounds, and organyls, in particular methyl compounds, of the aforementioned doping elements are suitable.
  • solutions, in particular liquid solutions of salts of the abovementioned compounds, which are described in more detail below, can also be used as doping reagents.
  • the precursors in particular the mixture of gaseous and / or liquid carbon or silicon sources, furthermore have at least one alloying reagent, preferably for the production of silicon carbide alloys.
  • alloying reagents according to this embodiment are - as already stated in connection with the doping reagents - in particular gaseous and / or liquid alloying reagents of advantage, in particular highly volatile compound of the aforementioned metals can be used.
  • the alloying reagent is preferably a liquid, gaseous and / or highly volatile compound selected from the group of Al, Ti, V, Cr, Mn, Co, Ni, Zn, Zr and mixtures thereof.
  • the hydrides and organyls, in particular methyl compounds, of the abovementioned metals are suitable as conductive alloying reagents in this connection.
  • alloying reagents it is also possible to use solutions, in particular liquid solutions of salts of the abovementioned metals, which are also described in greater detail below, as likewise already carried out within the scope of the doping reagents.
  • the precursors are in the form of carbon sources and solutions or dispersions containing silicon sources, in particular in the form of precursor sols.
  • a precursor sol is a solution or dispersion of precursor substances, in particular starting compounds, preferably precursors, which react to give the desired target compounds.
  • the chemical compounds or mixtures of chemical compounds are no longer necessarily present in the form of the originally used chemical compounds, but instead, for example, as hydrolysis, condensation or other reaction or intermediate products.
  • this is made clear in particular by the expression of the "sol".
  • sol-gel processes are usually inorganic materials under hydro- or solvolysis into reactive intermediates or agglomerates and particles, the so-called sol, transferred, which then age in particular by condensation reactions to a gel, with larger particles and agglomerates formed in the solution or dispersion.
  • a SiC precursor sol is understood as meaning both a sol and a gel, in particular a solution or dispersion, which contains chemical compounds or their reaction products from which materials containing silicon carbide can be obtained under process conditions.
  • a solution is to be understood as meaning a usually liquid single-phase system in which at least one substance, in particular a compound or its components, such as ions, are homogeneously distributed in another substance, the so-called solvent.
  • a dispersion is to be understood as meaning an at least two-phase system in which a first phase, namely the dispersed phase, is distributed in a second phase, the continuous phase.
  • the continuous phase is also referred to as a dispersion medium or dispersant;
  • the continuous phase is usually present in the form of a liquid in the context of the present invention, and dispersions in the context of the present invention are generally solid-in-liquid dispersions.
  • sols and gels in particular, as in the case of polymeric compounds, the transition from a solution to a dispersion is often fluid and it is no longer possible to clearly distinguish between a solution and a dispersion.
  • the solution or dispersion containing the carbon and silicon sources, in particular the precursor sol contains
  • the solution or dispersion containing the carbon and silicon source in particular the SiC precursor sol, contains Compounds which release silicon under process conditions and compounds which release carbon under process conditions.
  • the ratio of carbon to silicon in the solutions containing carbon and silicon sources or dispersions can be easily varied and tailored to the respective applications.
  • the silicon-containing compounds according to this embodiment of the present invention correspond to carbon sources and silicon sources as defined above.
  • the compounds used should have sufficiently high solubilities in the solvents used, in particular in ethanol and / or water, in order to be able to form finely divided dispersions of the solutions, in particular sols, and must not be mixed with other components of the solution during the preparation process Dispersion, in particular of the sol, react to insoluble compounds.
  • reaction rate of the individual reactions occurring must be coordinated, since the hydrolysis, condensation and optionally gelation should proceed as possible undisturbed in order to obtain the most homogeneous possible distribution of the individual components in the sol.
  • formed reaction products must not be sensitive to oxidation and, moreover, should not be volatile.
  • solvent or dispersant in the solution containing carbon and silicon sources this may be selected from any suitable solvent or dispersant.
  • the solvent or dispersing agent is selected from water and organic solvents and mixtures thereof.
  • the starting compounds which are generally hydrolyzable or may be hydrolysed are converted into inorganic hydroxides, in particular metal hydroxides and silicic acids, which subsequently condense, so that precursors suitable for pyrolysis and crystallization are obtained.
  • the organic solvent is selected from alcohols, in particular methanol, ethanol, 2-propanol, acetone, ethyl acetate and mixtures thereof. It is particularly preferred in this context if the organic solvent is is selected from methanol, ethanol, 2-propanol and mixtures thereof, in particular ethanol is preferred.
  • organic solvents are miscible with water over a wide range and, in particular, are also suitable for dispersing or for dissolving polar inorganic substances, for example metal salts.
  • mixtures of water and at least one organic solvent are preferably used as solvents or dispersants.
  • the solvent or dispersing agent has a weight-related ratio of water to organic solvent of 1:10 to 20: 1, in particular 1: 5 to 15: 1, preferably 1: 2 to 10: 1, preferably 1 : 1 to 5: 1, more preferably 1: 3.
  • the rate of hydrolysis in particular of the silicon-containing compound and of the doping reagents, can be adjusted by the ratio of water to organic solvents; on the other hand, the solubility and reaction rate of the carbon-containing compound, in particular of the carbonaceous precursor compound, such as, for example, sugar, can be adjusted.
  • the amount in which the composition contains the solvent or dispersant may vary widely depending on the particular application conditions and the nature of the doped or undoped silicon carbide or non-stoichiometric silicon carbide or silicon carbide alloy to be produced.
  • the composition comprises the solvent or dispersant in amounts of 10 to 80 wt .-%, in particular 15 to 75 wt .-%, preferably 20 to 70 wt .-%, preferably 20 to 65 wt .-%, based on the composition, on.
  • the silicon-containing compound is selected from silanes, silane hydrolyzates, orthosilicic acid and mixtures thereof, in particular silanes.
  • Orthosilicic acid and its condensation products can be obtained in the context of the present invention, for example, from alkali metal silicates whose alkali metal ions have been exchanged by ion exchange for protons.
  • alkali metal compounds are as far as possible not used in the composition since they also belong to the silicon carbide-containing compound be stored.
  • alkali metal doping is generally undesirable in the context of the present invention.
  • suitable alkali metal salts for example, the silicon-containing compounds or alkali phosphates, may be used.
  • silane is used as the silicon-containing compound in the context of the present invention, it has proven useful if the silane is selected from silanes of the general formula II
  • R alkyl, in particular C 1 - to C 6 -alkyl, preferably C 1 to C 3 -alkyl, preferably C 1 - and / or C 2 -alkyl;
  • Aryl in particular C 6 - to C 2 o-aryl, preferably C 6 - to C 5 -aryl, is preferred
  • Olefin in particular terminal olefin, preferably C 2 - to C-io-olefin, preferably C 2 - to Cs-olefin, more preferably C 2 - to C 5 olefin, most preferably C 2 - and / or C3-olefin, particularly preferably vinyl;
  • Amine in particular C 2 - to do-amine, preferably C 2 - to Cs-amine, preferably C 2 - to C 5 -amine, more preferably C 2 - and / or C 3 -amine;
  • Carboxylic acid in particular C 2 - to Cm-carboxylic acid, preferably C 2 - to Cs-carboxylic acid, preferably C 2 - to C 5 carboxylic acid, particularly preferably C 2 - and / or C 3 -carboxylic acid;
  • Alcohol in particular C 2 - to C 6 -alcohol, preferably C 2 - to Cs-alcohol, preferably C 2 - to C 5 -alcohol, more preferably C 2 - and / or C 3 -alcohol;
  • X halide, in particular chloride and / or bromide
  • Alkoxy in particular Cr to C6-alkoxy, particularly preferably Cr to C 4 - alkoxy, very particularly preferably Cr and / or C 2 -alkoxy;
  • n 1 - 4, preferably 3 or 4.
  • silane is selected from silanes of the general formula I Ia
  • R Cr to C 3 -alkyl, in particular Cr and / or C 2 -alkyl;
  • n 3 or 4.
  • the silicon-containing compound is selected from tetraalkoxysilanes, trialkoxysilanes and mixtures thereof, preferably tetraethoxysilane, tetramethoxysilane or triethoxymethylsilane and mixtures thereof.
  • the solution containing the carbon and silicon sources contains the silicon-containing compound
  • the silicon-containing compound in amounts of 1 to 80 wt .-%, in particular 2 to 70 wt .-%, preferably 5 to 60 wt .-%, preferably 10 to 60 wt .-%, based on the solution or dispersion on.
  • the solution or dispersion of the invention containing the carbon and silicon sources contains at least one carbon-containing compound.
  • the carbon-containing compound are all compounds into consideration, which can either dissolve in the solvents used or at least finely dispersed and can release solid carbon in the pyrolysis.
  • the carbonaceous compound is also capable of reducing metal hydroxides to elemental metal under process conditions.
  • the carbon-containing compound is selected from the group of sugars, in particular sucrose, glucose, fructose, invert sugar, maltose; Strength; Starch derivatives; organic polymers, in particular phenol-formaldehyde resin and resorcinol-formaldehyde resin, and mixtures thereof.
  • sugars in particular sucrose, glucose, fructose, invert sugar, maltose; Strength; Starch derivatives; organic polymers, in particular phenol-formaldehyde resin and resorcinol-formaldehyde resin, and mixtures thereof.
  • the amount in which the carbon or silicon sources containing solution or dispersion contains the carbonaceous compound may also vary widely depending on the particular application and application conditions or the target compounds to be prepared.
  • the solution or dispersion contains the carbonaceous compound in amounts of 5 to 50 wt .-%, in particular 10 to 40 wt .-%, preferably 10 to 35 wt .-%, preferably 12 to 30 wt .-%, based on the solution or dispersion.
  • the composition optionally has a doping or alloying reagent.
  • the composition when the composition comprises a doping or alloying reagent, the composition usually comprises the doping agent or alloying reagent in amounts of from 0.000001 to 60% by weight, in particular 0.000001 to 45% by weight, preferably 0.000005 to 45% by weight. -%, preferably 0.00001 to 40 wt .-%, based on the solution or dispersion, on.
  • doping and alloying reagents can decisively change the properties of the resulting silicon carbide-containing compounds.
  • the electrical properties of the silicon carbide-containing compound are influenced by doping, whereas the production of silicon carbide alloys or non-stoichiometric silicon carbides decisively influences the mechanical and thermal properties of the compounds containing silicon carbide.
  • the constituents of the individual components of the composition according to the invention vary widely depending on the respective application conditions and the silicon carbide-containing compounds to be prepared in each case.
  • silicon carbide-containing compounds to be prepared in each case.
  • there are great differences for example, whether a stoichiometric, optionally doped, silicon carbide, a non-stoichiometric silicon carbide or a silicon carbide alloy to be produced.
  • suitable doping reagents may be added to the solution or dispersion, in particular the precursor sol.
  • the doping reagents-like the alloying reagents-are decomposed during the process so that the desired elements react as reactive particles to the desired optionally doped silicon carbide, while the remaining constituents of the compound Possibility of stable gaseous substances, such as water, CO, C0 2 , HCl, etc., react, which can be easily removed via the gas phase.
  • the compounds used should moreover have sufficiently high solubilities in the solvents used, in particular in ethanol and / or water, to be able to form finely divided dispersions or solutions, in particular sols, and must not be mixed with other constituents of the solution or dispersion during the preparation process , in particular the sol, react to insoluble compounds.
  • the silicon carbide is to be doped with nitrogen, then, for example, nitric acid, ammonium chloride or melamine can be used as doping reagents.
  • nitrogen it is also possible to carry out the process for producing the silicon carbide in a nitrogen atmosphere, wherein doping with nitrogen can also be achieved, but which are less accurate.
  • the doping reagent is selected from arsenic trichloride, antimony chloride, arsenic oxide or antimony oxide. If aluminum is to be used as doping reagent, aluminum powder may be used as doping, in particular in the case of an acidic or basic pH. In addition, it is also possible to use aluminum chlorides.
  • the doping element When using metals as doping element, it is generally possible to use the chlorides, nitrates, acetates, acetylacetonates, formates, alkoxides and hydroxides, with absorption of sparingly soluble hydroxides. If boron is used as the doping element, then the doping element is usually boric acid.
  • the doping reagent is usually selected from indium halides, in particular indium trichloride (lnCl 3 ).
  • the doping reagent is usually selected from gallium halides, in particular GaC.
  • the composition usually comprises the doping reagent in amounts of 0.000001 to 15% by weight, in particular 0.000001 to 10% by weight, preferably 0.000005 to 5 wt .-%, preferably 0.00001 to 1 wt .-%, based on the solution or dispersion on.
  • doping reagents can decisively change the properties of the resulting silicon carbide.
  • the composition contains the silicon-containing compounds in amounts of from 20 to 40% by weight, in particular from 25 to 35% by weight, preferably 30 to 40 wt .-%, based on the composition contains.
  • the solution or dispersion contains the carbon-containing compound in amounts of from 20 to 40% by weight, in particular from 25 to 40% by weight, preferably from 25 to 35% by weight, preferably 25 to 35 wt .-%, based on the composition contains.
  • the composition contains the solvent or dispersant in amounts of from 30 to 80% by weight, in particular from 35 to 75% by weight, preferably from 40 to 70% by weight, preferably from 40 to 65 Wt .-%, based on the composition contains.
  • composition according to this embodiment contains a doping reagent, in particular selected from the abovementioned compounds and / or in the amounts mentioned in connection with the doped silicon carbides.
  • the ratio of silicon to carbon in the solution containing the carbon and silicon sources or dispersion for the production of an optionally doped stoichiometric silicon carbide is concerned, this can of course vary within wide ranges.
  • the solution containing carbon and silicon sources, in particular the SiC precursor sol has a weight-related ratio of silicon to carbon in the range from 1: 1 to 1:10, in particular 1: 2 to 1: 7, preferably 1: 3 to 1: 5, preferably 1: 3.5 to 1: 4.5.
  • the weight-based ratio of silicon to carbon in the solution containing carbon and silicon sources or dispersion, in particular in the SiC precursor sol is 1: 4.
  • the composition usually contains the silicon-containing compound in amounts of from 20 to 70% by weight, in particular from 25 to 65% by weight. %, preferably 30 to 60 wt .-%, preferably 40 to 60 wt .-%, based on the composition.
  • the composition contains the carbonaceous compound in amounts of 5 to 40% by weight, in particular 10 to 35% by weight, preferably 10 to 30% by weight, preferably 12 to 25% by weight. -%, based on the composition contains.
  • the composition contains the solvent or dispersant in amounts of from 30 to 80% by weight, in particular from 35 to 75% by weight. , preferably 40 to 70 wt .-%, preferably 40 to 65 wt .-%, based on the composition contains.
  • compositions for producing a silicon carbide alloy contains the silicon-containing compound in amounts of 1 to 80% by weight, in particular 2 to 70% by weight, preferably 5 to 60 wt .-%, preferably 10 to 30 wt .-%, based on the composition contains.
  • the composition contains the carbon-containing compound in amounts of 5 to 50% by weight, in particular 10 to 40% by weight, preferably 15 to 40% by weight, preferably 20 to 35% by weight. -%, based on the composition contains.
  • the composition, the solvent or dispersant in amounts of 10 to 60 wt .-%, in particular 15 to 50 wt .-%, preferably 15 to 40 wt .-%, preferably 20 to 40 Wt .-%, based on the composition contains.
  • the composition contains the alloying reagent in amounts of from 5 to 60% by weight, in particular from 10 to 45% by weight, preferably from 15 to 45% by weight, preferably from 20 to 40 Wt .-%, based on the composition contains.
  • the alloying reagent is selected from the corresponding chlorides, nitrates, acetates, acetylacetonates and formates of the alloying elements, in particular alloying metals.
  • the alloying element or metal is usually selected from the group of Al, Ti, V, Cr, Mn, Co, Ni, Zn, Zr and mixtures thereof.
  • the precursors it is customary for the precursors to be introduced into the reactor in fine distribution, in particular to be deposited. Due to a fine distribution of the precursors a rapid decomposition of gaseous precursors or a rapid and complete transfer of liquid is achieved. achieved precursors in the gas phase, so that the precursors are completely and rapidly decomposed into reactive species.
  • the substrate may be selected from a variety of suitable materials and objects.
  • the substrate is selected from metal substrates, in particular metal foils or metal plates, graphite substrates, in particular graphite plates and / or graphite fibers, carbon nanotubes, carbon fiber-reinforced plastic plates, ceramic substrates, silicon carbide substrates and mixtures thereof.
  • metal substrates in particular metal foils or metal plates
  • graphite substrates in particular graphite plates and / or graphite fibers, carbon nanotubes, carbon fiber-reinforced plastic plates
  • ceramic substrates silicon carbide substrates and mixtures thereof.
  • silicon carbide substrates preferably substrates with a very flat surface, such as, for example, metals or metal foils, ceramic plates or silicon carbide substrates, are provided, whereas separate, d. H. isolated, silicon carbide-containing fibers are preferably produced on structured substrates, in particular graphite plates and / or graphite fibers, carbon nanotubes, carbon fiber-reinforced plastic plates or structured silicon
  • the metals of the metal substrates are in particular precious metals and their alloys, in particular copper, silver, gold, platinum and their alloys, copper being preferred.
  • the process is carried out in a protective gas atmosphere, in particular in an inert gas atmosphere.
  • a protective gas is to be understood as meaning a gas which, in particular, prevents the oxidation of carbon and silicon by atmospheric oxygen, in particular the formation of silicon dioxide and carbon monoxide or carbon dioxide.
  • a protective gas may possibly participate in the formation reaction of the silicon carbide itself and be incorporated as a doping in the silicon carbide structure.
  • an inert gas is to be understood as meaning a gas which is completely inert under reaction conditions and does not undergo any reaction with the precursors or with their decomposition and reaction products.
  • nitrogen is a protective gas, but not an inert gas, since nitrogen can be incorporated at the prevailing high temperatures in the form of dopants into the Siliziumcarbidgestige.
  • argon is not only a shielding gas, but also an inert gas, as it is not involved in the reactions.
  • the process is carried out in a protective gas atmosphere, it has proven useful if the protective gas is selected from nitrogen and noble gases, in particular argon. Particularly good results are obtained in this context if the protective gas is selected from nitrogen and argon, in particular argon.
  • the pressure at which the method according to the invention is carried out this can also vary within wide ranges. Usually, however, the process is carried out at atmospheric pressure or under pressure. Under atmospheric pressure is to be understood in the context of the present invention, the ambient pressure, which varies slightly by the range of 1, 013 bar.
  • the temperatures in the first temperature zone of the reactor to 1, 500 to 2,100 ° C, in particular 1 .600 to 2,000 ° C, preferably 1 .700 to 1,900 ° C, are set.
  • the temperature in the second zone of the reactor 50 to 300 ° C, in particular 80 to 250 ° C, preferably 100 to 200 ° C, set lower for the preparation of the silicon carbide-containing fibers is considered in the first zone of the reactor.
  • the temperatures in the second zone of the reactor are in the range of from 1,200 to 2,000 ° C., in particular 1,500 to 1,900 ° C., preferably 1 .600 to 1 .800 ° C, can be set.
  • the temperatures in the first zone of the reactor to values in the range of 1 .100 to 1 .800 ° C, in particular 1 .200 to 1 .600 ° C, preferably 1 .300 to 1, 500 ° C, are set.
  • the temperatures in the second zone of the reactor to values in the range of 1, 000 to 1, 500 ° C, in particular 1, 050 to 1 .400 ° C, preferably 1 .100 to 1 .250 ° C, are set.
  • FIG. 1 shows a device according to the invention for the production of silicon carbide-containing fibers or silicon carbide-containing nano- and / or microstructured foams
  • FIG. 2 shows a device according to the invention for acting on fabrics with nano- and / or microstructured silicon carbide foams
  • FIG. 3 shows a photograph of a nano- and / or microstructured silicon carbide foam in 100-fold magnification
  • FIG. 4 shows a photograph of a nano- and / or microstructured silicon carbide foam in 35,000 times magnification.
  • Another object of the present invention - according to a z w e i t e an aspect of the present invention - are silicon carbide-containing fibers, which are obtainable by the method described above.
  • the silicon carbide-containing fibers according to the invention are outstandingly suitable as reinforcements or reinforcement, for example in plastics or building materials, such as, for example, plasters, in order to achieve their respective mechanical properties. Shafts to improve.
  • the silicon carbide-containing fibers can also be used for composite materials, for example in lightweight applications or translucent composite glasses.
  • the silicon carbide fibers or doped silicon carbide can be used in an excellent manner as anode materials for lithium-ion secondary batteries.
  • the fibers can be processed with binders and optionally with conductivity improvers, such as Leitru hybrid, to electrodes, in particular anode materials.
  • Another object of the present invention - according to an aspect of the present invention - is the use of the above-described silicon carbide-containing fibers for the production of composite materials, in particular for lightweight construction applications or laminated glass, and / or as a reinforcing filler.
  • the silicon carbide-containing fibers according to the invention in particular individual, d. H. separate silicon carbide-containing fibers are used as reinforcement or reinforcement in the composite materials. This applies in particular to fibers based on non-stoichiometric silicon carbides and silicon carbide alloys.
  • Another object of the present invention - according to one aspect of the present invention - is the use of the previously described silicon carbide-containing fibers, in particular silicon carbide fibers, for the production of anodes and / or as anode material.
  • the silicon carbide fibers are used in particular as anode materials for lithium-ion batteries.
  • Another object of the present invention - according to a fifth aspect of the present invention - are silicon carbide-containing nano- and / or microstructured foams, obtainable by the method described above.
  • the specific surface area of the silicon carbide-containing foams obtainable by the process according to the invention is usually in the range from 15,000 to 70,000 m 2 / m 3 , in particular from 20,000 to 60,000 m 2 / m 3 , preferably from 25,000 to 50,000 m 2 / m 3 .
  • the specific gravity of the silicon carbide-containing foams obtainable by the process according to the invention is in the range from 0.01 to 0.8 g / cm 3 , in particular from 0.05 to 0.6 g / cm 3 , preferably from 0, 1 to 0.5 g / cm 3 .
  • the silicon carbide-containing foams obtainable by the process according to the invention are highly resistant to thermal, chemical and mechanical stress and have excellent electrical properties. Not only do they withstand temperatures of up to 1,600 ° C and high pressure loads without destruction, they also retain their good electrical properties after a large number of charging and discharging cycles with lithium ions. They are suitable for all applications in which permanently elastic materials are used.
  • the silicon carbide-containing nano- or microstructured foams according to the invention can also be used in an outstanding manner as sealants.
  • Insulation materials in particular for the absorption of vibration and / or sound are used, and as a material for suspensions, springs or damping.
  • materials based on non-stoichiometric silicon carbides or silicon carbide alloys are suitable for the abovementioned applications, while optionally doped silicon carbide is used for electrical or electronic applications.
  • Another object of the present invention - according to a sixth aspect of the present invention - is the use of silicon carbide-containing nano- and / or microstructured foams in seals, suspensions, suspensions, dampers, insulation, in particular for the absorption of vibration and / or sound, membranes or filters ,
  • Another object of the present invention - according to one aspect of the present invention - is the use of silicon carbide-containing nano- and / or microstructured foams, in particular nano- and / or microstructured silicon carbide foams, as described above for the production of anodes and / or as anode material.
  • Another object of the present invention - according to an aspect of the present invention - is an apparatus for the production of silicon carbide-containing fibers or silicon carbide-containing nano- and / or microstructured foams, wherein the device
  • temperatures in the two temperature zones in particular independently of one another, can be regulated, in particular by a control unit,
  • At least one introduction device in particular injection device, for introduction, in particular injection, of gaseous and / or liquid precursors containing at least one carbon source and at least one at least one silicon source and optionally doping reagents, in the first temperature zone of the reactor and
  • the first temperature zone of the reactor is also referred to as the reaction zone, since here the precursors or reactive species are formed from the precursors, which are subsequently deposited on the substrate as silicon carbide-containing compound, in particular as silicon carbide.
  • the second temperature zone of the reactor is also called the SiC-forming zone, since first condensations of the reactive species formed during the decomposition of the precursors already take place in this zone.
  • the temperature in the first temperature zone in the range of 1 .100 to 2,100 ° C., in particular 1 .200 to 2,000 ° C., preferably 1 .200 to 1,900 ° C. is controllable.
  • a temperature gradient between the first and the second temperature zone is adjustable, in particular wherein the temperature in the second temperature zone can be set lower than in the first temperature zone.
  • the temperature in the reactor can be controlled such that the temperature gradient in the reactor continues to the substrate so that the substrate has the lowest temperature surface in the reactor and silicon carbide-containing fibers and foams, especially silicon carbide fibers or silicon carbide foams, precipitate exclusively on the substrate.
  • the substrate is usually in the second temperature zone of the reactor. In order to achieve that the substrate has a relation to the second temperature zone has again lower temperature, can be dispensed with heaters in the vicinity of the substrate or the substrate moved through the reactor, in particular continuously moved. This is especially true if the substrate can be moved out of the reactor or if the residence time of the substrate in the reactor is only very short. It is also possible that the substrate is specially tempered, as will be explained below.
  • a temperature control of the substrate is particularly advantageous if the substrate consists of metal, in particular a metal foil. If the substrate is made of metal, in particular a metal foil, it has proven useful if the substrate temperature is not higher than 1 .000 ° C, in particular not higher than 950 ° C, preferably not higher than 900 ° C. Particularly good results are obtained in this context if the substrate temperature in the range of 700 to 1 000 ° C, in particular 800 to 950 ° C, preferably 850 to 900 ° C, in particular is adjustable.
  • the reactor has at least one heating device, in particular in the region of the first temperature zone.
  • the reactor has at least one heating device in both the first and second temperature zones.
  • the type of heater As far as the type of heater is concerned, it may be selected from a variety of heaters. In the context of the present invention, however, it has proven useful if the heating device is selected from microwave radiators, infrared radiators, radiant heaters, electrical resistance heaters and their combinations, in particular microwave radiators, electrical resistance heaters and their combinations.
  • the aforementioned heaters all allow a very continuous and above all a very rapid heating of the liquid and / or gaseous precursors and their rapid decomposition.
  • the reactor comprises at least one transport device for transporting the substrate in the reactor, in particular through the reactor, preferably through the second temperature zone of the reactor, and in particular for introduction into and removal of the substrate having the reactor.
  • a transport device for moving the substrate through the reactor on the one hand, a low temperature of the substrate can be obtained in a very simple manner. be aimed, since the residence time of the substrate is shortened in the reactor, so that the substrate has already left the reactor again, before it has fully heated to the prevailing temperatures in the second temperature zone of the reactor temperatures.
  • this embodiment also makes possible a continuous process management, in particular continuous application of a substrate with silicon carbide-containing fibers or silicon carbide-containing nano- and / or microstructured foams, in particular silicon carbide fibers or nano- and / or microstructured silicon carbide foams.
  • Such a lock system also allows a continuous process, in which substrate is constantly introduced into the reactor and coated substrate is discharged from the reactor.
  • the reactor and / or the transport device has a temperature device for controlling the temperature of the substrate.
  • a temperature device for controlling the temperature of the substrate.
  • tempering the temperature of the substrate can be adjusted accurately.
  • thin metal foils for example, can be prevented from being damaged or melting at the temperatures prevailing in the second temperature zone of the reactor of often more than 1 .000 ° C., for example.
  • Yet another subject of the present invention - according to a n e n e n e aspect of the present invention - is a method for applying a sheet with a nano- and / or microstructured silicon carbide foam, in particular method for producing an electrode, wherein
  • the temperatures in the first temperature zone of the reactor to values in the range of 1 .100 to 1 .800 ° C, in particular 1 .200 to 1 .600 ° C, preferably 1 .300 to 1, 500 ° C.
  • the temperature in the second zone of the reactor is set to 30 to 200.degree. C., in particular 40 to 150.degree. C., preferably 50 to 100.degree. C., lower than in the first Zone of the reactor.
  • the temperature regime thus preferably corresponds to that previously described in connection with the process according to the invention for producing silicon carbide-containing nano- and microstructured foams.
  • a sheet-like structure in particular a metallic sheet, is understood to mean a nearly two-dimensional object, in particular of metal, in particular a metal foil or a metal sheet.
  • the sheet contains or preferably consists of ceramic, in particular silicon carbide, graphite or at least one metal.
  • nano- and / or microstructured SiliziumcarbidCume can be deposited directly on fabrics, so that binder-free electrode materials, in particular anodes, for lithium-ion batteries are accessible in a simple manufacturing process.
  • the direct application of silicon carbide foams, in particular foams of doped silicon carbide, to metals, in particular metal foils or metal sheets, makes it possible to produce highly porous and highly conductive anodes for lithium-ion accumulators which do without the use of binders which are used in prior art anode systems for fixing of graphite, tin or silicon particles are needed.
  • bipolar electrodes When using ceramic or graphite sheets, it is possible to produce bipolar electrodes which can be placed directly in stacks and eliminate the need for external electrical connection of individual cells.
  • the use of bipolar electrodes and the stacks obtainable with them have considerable advantages over conventional electrical cells in terms of volume, manufacturing technology and cost.
  • a derivative over ceramic, such as silicon carbide, or graphite is sufficient, so that nano- and / or microstructured SiliziumcarbidFiume as anode materials directly to a collector can be applied from ceramic materials or graphite. Subsequently, a cathodic layer is applied, so that a bipolar electrode is obtained.
  • the electrodes produced by the method according to the invention are distinguished from the prior art electrodes by increased thermal and mechanical strength, since the monocrystalline or nanocrystalline silicon carbide foams can be thermally stressed up to about 1600 ° C. and above Although the foam is dimensionally stable and very pressure-resistant, but it is flexible enough not to break at high local pressure, but to deform elastically and return to its original state after completion of the pressure load.
  • the high porosity of the electrode materials obtainable by the method according to the invention, in particular anodes allows a complete penetration of the foam structure with the electrolyte of a lithium-ion secondary battery, so that the high storage potential of the silicon carbide fibers for lithium ions can actually be fully utilized.
  • the sheet is a metallic sheet, in particular a metal sheet or metal foil.
  • the material of the metallic fabric it can be selected from all suitable metals and their alloys, with particular attention being paid to high electrical conductivity.
  • the metal of the metallic sheet is a noble metal or a noble metal alloy.
  • particularly good results are obtained when the metal of the metal sheet is selected from copper, silver, gold, platinum and their alloys.
  • the use of copper is particularly preferred because copper not only has excellent electrical conductivity, but in comparison to the other precious metals is comparatively low and is available in large quantities.
  • the sheet generally has a thickness of 1 to 1 .mu.m, in particular 5 to 100 .mu.m, preferably 10 to 20 .mu.m.
  • the thickness of the sheet in particular if it is in the form of a foil or a sheet, is thus negligible compared to the width, which can be up to 50 cm or more, and the length, which can be up to several meters or even kilometers ,
  • the metal sheet is in the form of a band or in the form of plates, in particular a graphite or metal strip.
  • the method can be operated continuously.
  • ceramic materials for the sheet in particular, the use of plates, which are preferably moved through the reactor, in order to achieve the most uniform coating of the plates.
  • the fabric is coated in sections and / or continuously with the nano- and / or microstructured silicon carbide foam. It is particularly preferred in this context if the fabric is continuously No- and / or microstructured silicon carbide foam is coated.
  • the sheet is moved through the reactor, in particular continuously moved through the reactor.
  • a movement in particular a continuous movement of the fabric through the reactor, in particular through the second temperature zone of the reactor, it is possible even thin films of metals with a low melting point, such as copper foils, with nano- and / or microstructured SiliziumcarbidCumen possible without damaging or destroying the sheet since the residence time of the sheet in the reactor is reduced.
  • the movement of the sheet through the reactor also allows a simple way to create the coating thickness.
  • the metallic sheet is moved through the reactor, in particular moved continuously through the reactor, it is usually necessary to feed the sheet into and out of the reactor, in particular also in continuous operation.
  • suitable locks are familiar to the person skilled in the art and are known in the prior art.
  • the metallic sheet is usually at a speed of 0.05 to 2 m / s, in particular 0.08 to 1 m / s, preferably 0.1 to 0.5 m / s, moved through the reactor.
  • the inventive method can also be carried out on an industrial scale, so that in a short time a large number of electrodes, especially anodes, can be provided for lithium-ion batteries quickly.
  • the fabric in particular the metallicinstitungetrucke, is tempered in the reactor.
  • the sheet in the reactor may be provided that the sheet in the reactor to temperatures in the range of 700 to 1 000 ° C, in particular 800 to 950 ° C, preferably 850 to 900 ° C, tempered. Due to a special tempering of the fabric, For example, the underside of the fabric and metallic fabrics with a low melting point and a very small layer thickness can be applied to nano- and / or microstructured SiliziumcarbidTypeumen.
  • the deposition rate can also be influenced by the temperature of the substrate.
  • the sheet is applied from both sides with a nano- and / or microstructured silicon carbide foam, in particular by first applying one side of the sheet and then in a second reactor and / or at re-run of the reactor is applied to the other side of the sheet.
  • the area acted upon by the nano- and / or microstructured silicon carbide foam fabricated after application from the reactor By means of a fabrication, electrodes for lithium-ion accumulators are immediately obtained, which are ready for immediate use.
  • packaging prior to incorporation into storage batteries is indispensable.
  • suitable solid precursors With regard to the production of suitable solid precursors, reference is made in particular to International Application WO 2016/078955 A1, the content of which is hereby expressly also made the subject of the present invention.
  • the further process parameters in the application of fabrics with solid precursors correspond to those with the use of liquid and / or gaseous precursors.
  • a precursor granulate which preferably comprises the solution or dispersion containing carbon and silicon sources described in connection with the process according to the invention for producing silicon carbide fibers and nano- or microstructured silicon carbide foams , in particular the precursor sol, is available.
  • the precursor granules are obtainable by a sol-gel process.
  • sol-gel processes solutions or finely divided solid-in-liquid dispersions are usually prepared, which are converted by subsequent aging and the condensation processes occurring in the process into a gel which contains larger solid particles.
  • the reaction rate of each occurring in solution or dispersion reactions must be coordinated, since the hydrolysis, condensation and in particular the gelation must proceed undisturbed in the run-up to granule formation. Furthermore, the formed reaction products must not be sensitive to oxidation and, moreover, should not be volatile.
  • the duration of the drying is concerned, this can vary within wide ranges. However, it has proven useful if the reaction product of the gelation is dried for a period of 1 to 10 hours, in particular 2 to 5 hours, preferably 2 to 3 hours.
  • the precursor granules are comminuted, in particular following the drying process.
  • the reaction product is mechanically comminuted, in particular by grinding.
  • grinding processes it is possible to specifically set the particle sizes required or advantageous for the rapid gasification of the particles. Often, however, it is also sufficient to mechanically stress the reaction product of the gel during the drying process, for example by stirring to adjust the desired particle sizes.
  • the precursor granules are converted by thermal treatment under reductive conditions to a reduced precursor granules.
  • the reductive thermal treatment usually takes place in an inert gas atmosphere, wherein in particular the carbon source, preferably a sugar-based carbon source, reacts with oxides or other compounds of the silicon and any other compounds of other elements, in particular the doping elements, whereby the elements are reduced and volatile oxidized carbon and hydrogen compounds, especially water and C0 2 , arise, which are removed via the gas phase.
  • the carbon source preferably a sugar-based carbon source
  • the precursor granules are at temperatures in the range from 700 to 1,300 ° C., in particular 800 to 1,200 ° C., preferably 900 to 1 .100 ° C, heated.
  • the reducing treatment of the precursor granules is carried out in a protective gas atmosphere, in particular in an argon and / or nitrogen atmosphere. re, performed. In this way it is prevented that in particular the carbonaceous compound is oxidized.
  • the precursor compounds must not evaporate at the temperatures used of up to 1, 300, preferably up to 1, 100 ° C., but must Under the reductive thermal conditions, targeted decomposition to compounds which can be converted in the production of silicon carbide fibers and foams to the desired silicon carbide-containing compounds.
  • a further subject of the present invention - according to one of the aspects of the present invention is an electrode obtainable by the method described above.
  • an electrode obtainable by the method described above.
  • Yet another subject of the present invention - according to one aspect of the present invention - is an electrode comprising a sheet and a nano- and / or microstructured silicon carbide foam.
  • electrodes in particular anodes, which have only a flat structure, in particular a metallic sheet, and a nano- and / or microstructured silicon carbide foam.
  • the metallic sheet is subjected to the nano- and / or microstructured silicon carbide foam.
  • the electrode is in particular at least substantially free of binders.
  • the efficiency of the electrode according to the invention can be significantly increased in comparison to prior art electrodes, since the electrode material, with the exception of the discharge plate or the collector of ceramic material or graphite, consists solely of silicon carbide foams or fibers which contain lithium ions record and release again. By appropriate doping and the conductivity of the silicon carbide can be adjusted so that no conductivity improvers are needed.
  • the electrode consists of a particularly prefabricated fabric, in particular metallic fabric, and a nano- and / or microstructured silicon carbide foam.
  • Another object of the present invention - according to a z wöl f f ee aspect of the present invention - a lithium-ion secondary battery, comprising an aforementioned electrode, in particular anode.
  • the lithium-ion secondary battery according to the invention can be designed, for example, as a stack of bipolar electrodes, as stated above.
  • this aspect of the invention reference may be made to the above remarks on the other aspects of the invention, which apply correspondingly with respect to the lithium ion secondary battery according to the invention.
  • another object of the present invention is - according to one of the aspects of the present invention - a device for applying a sheet with a nano- and / or microstructured silicon carbide foam, in particular a device for producing an electrode, wherein the device
  • temperatures in the two temperature zones in particular independently of one another, can be regulated, in particular by a control unit,
  • the sheet in particular a metallic sheet
  • a continuous movement of the sheet through the second temperature zone of the reactor in particular by a continuous movement of the sheet through the second temperature zone of the reactor, and / or a temperature of the sheet is achieved that even thin metallic sheets with a low melting point can be coated with nano- and / or microstructured silicon carbide foams.
  • electrode materials in particular anode materials for lithium-ion accumulators, are accessible directly and without the use of binders.
  • the layer thickness of the silicon carbide foam on the sheet and the deposition rate of the silicon carbide foam can be adjusted.
  • the device for applying fabrics with nano- or microstructured silicon carbide foams moreover corresponds to the apparatus for producing the device described above for producing silicon carbide fibers or nano- and / or microstructured silicon carbide foams, wherein the substrate mentioned there corresponds to the fabric.
  • FIG. 1 shows a device 1 according to the invention for the production of silicon carbide-containing fibers or silicon carbide-containing nano- or microstructured foams.
  • the device 1 has a reactor 2 with a first temperature zone 3 and a second temperature zone 4.
  • the transition between the first and the second temperature zone is represented by the dashed line in the middle of the reactor 2. In fact, there is no sharp demarcation between the two temperature ranges, but rather preferably a temperature gradient is set in the reactor.
  • liquid or gaseous precursors 5, in particular also precursor sols are introduced into the reactor 2 by means of an introduction device 6, in particular an injection device, in particular into the first temperature zone 3.
  • the temperature in the reactor 2 is preferably set in such a way that from the introduction device 6 for introducing liquid and / or gaseous precursors 5 in the first temperature zone 3 to a substrate 7 for deposition of silicon carbide-containing fibers or foams, in particular silicon carbide fibers or Fiber foams 9, prevails in the second temperature zone 4, a temperature gradient, in particular wherein the temperature in the second temperature zone 4 is lower by preferably 30 to 300 ° C than in the first temperature zone third
  • the temperature in the first temperature zone 3 is usually 1 .100 to 2,100 ° C.
  • the heater 8 is preferably a microwave radiator or an electrical resistance heater.
  • the precursors 5 are decomposed and converted into reactive species.
  • the reactive species then diffuse into the somewhat cooler second temperature zone 4, where first agglomerates are formed which condense on the substrate 7 and form singulated silicon carbide fibers or a layer of silicon carbide foam 9.
  • SiliziumcarbidCumen 9 only the production of SiliziumcarbidCumen 9 is shown, wherein the production of separate fibers is completely analog, but at a different temperature regime.
  • the production of fibers and foams from other silicon carbide-containing materials, in particular silicon carbide alloys proceeds accordingly; For reasons of clarity, only the production of silicon carbide foams 9 will be described within the scope of the description of the figures.
  • the temperature gradient in particular the temperature gradient in the reactor is set such that the substrate 7 has the lowest temperature in the entire reactor 2, so that the silicon carbide fibers or the silicon carbide foams 9 are deposited exclusively on the substrate 7 ,
  • the temperature of a first temperature zone 3 of the reactor 2 is usually from 1 .100 to 1 .800 ° C., in particular from .200 to 1 .600 ° C., preferably from 1 .300 to 1, 500 ° C, and in contrast, in the second temperature zone 4 of the reactor 2 by about 50 to 100 ° C lower.
  • the temperature in the first temperature zone 3 of the reactor 2 is about 1600 to 2000 ° C and is in contrast lowered in the second temperature zone 4 by about 100 to 200 ° C.
  • the process for producing separate silicon carbide fibers as well as for producing nano- or microstructured silicon carbide foams is preferably carried out in an inert gas atmosphere, in particular an argon atmosphere.
  • FIG. 2 shows a special embodiment of the method according to the invention as well as the device 1 according to the invention for acting on fabrics with nano- or microstructured silicon carbide foams.
  • This special embodiment of the method according to the invention or of the device according to the invention is illustrated below on the basis of a metallic sheet, in which case it is likewise possible to use sheets of ceramic or graphite.
  • the device 1 has a reactor 2 with a first temperature zone 3 and a second temperature zone 4.
  • a temperature gradient is preferably present in the reactor 2, the temperature in the second temperature zone 4 in particular being lower than in the first temperature zone 3.
  • the temperature in the first temperature zone 3 is preferably from 1 .200 to 1 .600 ° C. and the temperature in the second temperature zone 4 is preferably lowered by 50 to 100 ° C in contrast.
  • the device 1 has at least one introduction device 6 for introducing solid, liquid and / or gaseous precursors 5 into the reactor 2.
  • the setting of the temperature zones in the reactor 2, in particular the heating of the precursors 5, takes place by means of heating devices 8, which are at least in the first temperature zone 3 of the reactor 2, but preferably both in the first temperature zone 3 and in the second temperature zone 4 of the reactor 2 are located.
  • the device 1 furthermore has lock devices 10 for the inward and outward transport of a metallic fabric 7a, in particular a metal foil or a metal sheet.
  • the device has at least one tempering device 1 1 for temperature control of the metallic fabric 7a.
  • the reactor 2 is preferably filled with an inert gas, in particular argon, and the process is preferably carried out in an inert gas atmosphere.
  • solid, liquid and / or gaseous precursors 5 are introduced into the reactor 2 in fine distribution by means of the introduction device 6, in particular into the first temperature zone of the reactor 2 and there to temperatures in the range of 1.200 to Heated to 1 600 ° C.
  • the introduction device 6 is preferably guided in the bottom of the reactor 2 and the metallic fabric 7 a and through the upper region of the reactor 2, which then lies in the second temperature zone 4. In this way it is prevented that non-gassed solid falls on the incorporated Siliziumcarbid Quilt or is incorporated into this.
  • it can be provided to convert the solid precursors 5 in an upstream chamber into a gaseous state, so that then, as already described, gaseous precursors 5 can be introduced into the reactor 2. By heating the precursors 5 they are decomposed and as completely as possible gasified, whereby reactive species are released, which diffuse into the second reaction zone 4 and form there first agglomerates in the gas phase.
  • the reactive species and agglomerates deposit in the form of a silicon carbide foam 9 on the metallic sheet 7a.
  • the temperature in the interior of the reactor 2 is controlled such that the temperature of the metallic sheet 7a in the second reaction zone 4 of the reactor 2 is below the temperature of the second temperature zone 4, so that the silicon carbide foam 9 is deposited exclusively on the metallic sheet 7 becomes.
  • the metallic sheet 7a is moved through the reactor 2, in particular the second temperature zone 4 of the reactor 2, so that a continuous coating or loading of the metallic sheet 7a with the nano- or micro-structured silicon carbide foam 9 is possible.
  • the device 1 has a tempering 1 1 for temperature control of the metallic sheet 7a.
  • a tempering 1 1 for temperature control of the metallic sheet 7a.
  • a mixture of tetrachlorosilane and butane is sprayed into the upper half of an argon-filled reactor with the temperatures in the upper half of the reactor being 1,300 and 1,800 ° C.
  • the temperatures are between 1 .100 and 1 .300 ° C.
  • a copper foil is moved at a feed rate of 0.1 m / s.
  • the copper foil has a width of about 10 cm and is in the form of a copper band.
  • the copper foil is kept at temperatures of 800 to 950 ° C.
  • a nano- or microstructured silicon carbide foam is deposited on its surface over an area of 30 ⁇ 10 cm. At the selected feed rate of 0, 1 m / s, this leads to the formation of a 10 ⁇ thick layer of silicon carbide foam
  • FIG. 4 shows a section of the silicon carbide foam produced by the process according to the invention at a magnification of 35,000 times. At this magnification, it can be clearly seen that the silicon carbide foam is an open cell foam and single silicon carbide fibers which are crosslinked together.

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  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Chemical Vapour Deposition (AREA)
  • Inorganic Fibers (AREA)

Abstract

La présente invention concerne un procédé de fabrication de fibres contenant du carbure de silicium ou de mousses nanostructurées et/ou microstructurées contenant du carbure de silicium, ainsi que l'utilisation de ces fibres et de ces mousses, en particulier comme matériaux d'anode dans des accumulateurs lithium-ion.
EP18740114.6A 2017-06-27 2018-06-25 Procédé de fabrication de fibres et de mousses contenant du carbure de silicium et utilisation de ces fibres et de ces mousses Withdrawn EP3645482A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017114243.6A DE102017114243A1 (de) 2017-06-27 2017-06-27 Verfahren zur Herstellung von siliciumcarbidhaltigen Fasern und Schäumen sowie ihre Verwendung
PCT/EP2018/066965 WO2019002211A2 (fr) 2017-06-27 2018-06-25 Procédé de fabrication de fibres et de mousses contenant du carbure de silicium et utilisation de ces fibres et de ces mousses

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EP3645482A2 true EP3645482A2 (fr) 2020-05-06

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US (1) US20200140281A1 (fr)
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JP (1) JP2020525648A (fr)
CN (1) CN110831912A (fr)
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WO (1) WO2019002211A2 (fr)

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CN113264753B (zh) * 2021-06-03 2023-02-03 哈尔滨工程大学 一种免加热型短碳化硅纤维增强磷酸盐复合材料的制备方法
CN113896201B (zh) * 2021-10-29 2022-07-19 连云港市沃鑫高新材料有限公司 一种电子封装用碳化硅粉体的制备方法
DE102021128398A1 (de) 2021-10-30 2023-05-04 The Yellow SiC Holding GmbH Siliziumkarbidhaltiges Material, Präkursor-Zusammensetzung und deren Herstellungsverfahren

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JPH02225677A (ja) * 1988-09-27 1990-09-07 Sumitomo Electric Ind Ltd 成膜方法
US5514350A (en) * 1994-04-22 1996-05-07 Rutgers, The State University Of New Jersey Apparatus for making nanostructured ceramic powders and whiskers
DE19713068A1 (de) * 1997-03-27 1998-10-01 Ecm Ingenieur Unternehmen Fuer Verfahren zur Herstellung von Heißgasfilter-Elementen sowie die Verwendung des Filters zur Heißgasfiltration von Rauchgasen
JP3661034B2 (ja) * 2001-11-15 2005-06-15 弘 中山 膜形成方法、膜、素子、アルキルシリコン化合物、及び膜形成装置
CN1210204C (zh) * 2003-07-15 2005-07-13 中国科学院理化技术研究所 一种制备碳化硅的方法
FR2860993B1 (fr) * 2003-10-16 2006-06-16 Sicat Filtre catalytique a base de carbure de silicium (b-sic) pour la combustion des suies issues des gaz d'echappement d'un moteur a combustion
JP4631472B2 (ja) * 2005-03-01 2011-02-16 株式会社ジェイテクト 被覆部材の製造方法
JP2013065496A (ja) * 2011-09-20 2013-04-11 Yoshiaki Nagaura シリコン二次電池アモルファス電極の高周波大気圧プラズマｃｖｄによる製造方法
JP2013171627A (ja) * 2012-02-17 2013-09-02 Bridgestone Corp 非水電解質二次電池用負極材及びリチウムイオン二次電池
CN103253672B (zh) * 2013-05-20 2014-11-26 浙江理工大学 基于光电催化分解水制氢的碳化硅纳米线薄膜制备方法
JP6079651B2 (ja) * 2014-01-15 2017-02-15 信越化学工業株式会社 非水電解質二次電池用負極材の製造方法
DE102014116868A1 (de) * 2014-11-18 2016-05-19 Universität Paderborn Verfahren zum Herstellen eines Elektrodenmaterials für eine Batterieelektrode
DE102015100062A1 (de) * 2015-01-06 2016-07-07 Universität Paderborn Vorrichtung und Verfahren zum Herstellen von Siliziumcarbid
DE102015103739A1 (de) * 2015-03-13 2016-09-15 Universität Paderborn Verfahren zum Herstellen einer Elektrode, Elektrode und Elektrolysevorrichtung
DE102015104943A1 (de) * 2015-03-31 2016-10-06 Universität Paderborn Verfahren zum Herstellen eines nano- oder mikrostrukturierten Schaumstoffs

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WO2019002211A3 (fr) 2019-02-21
US20200140281A1 (en) 2020-05-07
CN110831912A (zh) 2020-02-21
DE102017114243A1 (de) 2018-12-27
WO2019002211A2 (fr) 2019-01-03
JP2020525648A (ja) 2020-08-27

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