WO2001060593A2 - Method for the production of conductive composite material - Google Patents

Method for the production of conductive composite material Download PDF

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Publication number
WO2001060593A2
WO2001060593A2 PCT/NL2001/000137 NL0100137W WO0160593A2 WO 2001060593 A2 WO2001060593 A2 WO 2001060593A2 NL 0100137 W NL0100137 W NL 0100137W WO 0160593 A2 WO0160593 A2 WO 0160593A2
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WIPO (PCT)
Prior art keywords
polymer
conductive
mold
intermediate product
production
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Ceased
Application number
PCT/NL2001/000137
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French (fr)
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WO2001060593A3 (en
Inventor
Erik Middelman
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Nedstack Holding BV
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Nedstack Holding BV
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Priority to EP01910243A priority Critical patent/EP1299225A2/en
Priority to JP2001559673A priority patent/JP2003523066A/en
Publication of WO2001060593A2 publication Critical patent/WO2001060593A2/en
Publication of WO2001060593A3 publication Critical patent/WO2001060593A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0433—Molding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/34—Feeding the material to the mould or the compression means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/88—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced
    • B29C70/882—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • 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
    • H01M4/0483—Processes of manufacture in general by methods including the handling of a melt
    • 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
    • H01M4/64—Carriers or collectors
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
    • B29K2995/0005—Conductive
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention is related to a method for the production of sheet like material that can be used in applications were polymer based material has to conduct electric current at low impedance especially for application in electrodes like the electrodes of polymer electrolyte membrane (PEM) fuel cells the sheet material being electrically conductive composite material comprising a non conductive polymer binder and electrically conductive compounds
  • PEM fuel cell is comprises typically a proton conducting membrane with a catalyst-containing electrode on both sides Such an assembly is called a MEA (membrane electrode assembly)
  • MEA membrane electrode assembly
  • these MEA s ar placed between electrically conducting plates often called bi-polar plates to form a single fuel cell, or if more of these cells are stacked such a assembly is called a fuel cell stack
  • the mam functions of the bi-polar plates are conduction of elect ⁇ cal current from one electrode to another electrode of a in series connected fuel cell distribution of hydrogen and oxygen or an oxygen containing gas, removal of reaction water sealing between the gas channels and the atmosphere
  • Known bi-polar or mono poar plates are made from metal like stainless steel coated metal like gold-coated stainless steel, metal foam, synthetic graphite and conductive composite material Al these mate ⁇ als have their specific advantages and drawbacks as publicly known from several patents and many publications in the open literature Application of
  • DE 1995019542721 A method for the production of elect ⁇ cal conducive composite material for application in electrochemical cells, like fuel cells is disclosed in DE 1995019542721 According to this method a solid with good thermal conductivity and a polymer melt is mixed homogeneously Subsequently this powder is extruded to a tube like intermediate product This intermediate is according to the invention cut open and pressed flat to form a flat sheet like mate ⁇ al Application of the process according to DE 1995019542721 yields a product with a high content of conducting solid however this method has some serious drawbacks Homogeneous mixing of the polymer melt and the conductive solid is difficult if a high solid content is essential In addition to that the subsequent cooling and grinding is expensive An other drawback of the method of DE 1995019542721 is orientation during extrusion leading to non-isotropic material properties and a direction dependent coefficient of thermal expansion Not only the mechanical properties are affected, but also the electrical property like the conductivity perpendicular to the flow direction is usually reduced
  • the method according to this invention has as its objective to provide a method for large-scale production of electrical conductive sheet like material in which in which the disadvantages of the prior art are avoided
  • the process starts with powdered raw mate ⁇ als
  • a mixture is made comprising elect ⁇ cal conductive powder (material A) particles with a size of 10-300 micron, a second conductive powder (material B) has elementary particles of less than 1 micron, typically 0,2 micron, and the non-conductive polymer powder (material C) has a particle size between 0,1 and 500 micron
  • the mixture can also contain non conductive fibers, conductive fibers, whiskers, hydrophobing additives, additives for hydrophilisation, and other additives that improve process ability and or material properties
  • the polymer can be a thermoplastic polymer, a thermosetting polymer or an elastomer Suitable conductive fillers are metal powders, metal fibers, graphite, graphite fibers, carbon fibers, electrical conductive oxide powders like fluorine doped Tin oxide and Aluminum doped
  • the material can be kept under pressure for a certain time above the melting temperature of material C, attaining improved mechanical properties and less porosity.
  • the plate like material produced according to the process still contains some voids or porosity. These voids could have a negative influence on mechanical properties and electrical and thermal conductivity.
  • the process ability of the porous intermediate product is better than an intermediate with identical composition but no porosity.
  • the material is an intermediate product for the production of articles like electrode plates and plates of heat exchangers. In this forming process the intermediate material is heated to a temperature above the melting temperature of material C, placed in a compression mold and pressed. In this process the mold temperature is below the melting point of material C.
  • a second conductive powder (material B) has elementary particles of less than 1 micron, typically 0,2 micron
  • the non-conductive polymer powder (material C) has a particle size between 0,1 and 500 micron.
  • the mixture can also contain non conductive fibers, conductive fibers, whiskers, hydrophobing additives, additives for hydrophilisation, and other additives that improve procesability and or material properties.
  • the polymer can be a thermoplastic polymer, a thermosetting polymer or an elastomer.
  • Suitable conductive fillers are metal powders, metal fibers, graphite, graphite fibers, carbon fibers, electrical conductive oxide powders like fluorine doped Tin oxide and Aluminum doped zinc oxide, powders that are coated with a conductive layer and carbon blacks.
  • Suitable thermoplastic polymers are fluor polymers like PTFE, PVDF, PVF, PFA, FEP, THV, poly olefins like LD-PE, HD-PE, UHMWPE, PP, high temperature thermoplastics like PEN, PPS, PEI, PEEK.
  • the powders are preferably mixed below the melting point of material C.
  • the powder mixture is heated to a temperature just above the melting temperature of material C to cause some agglomeration, and thus avoiding demixing.
  • the powder mixture or the stabilized, agglomerated powder mixture is applied to a heated or heatable surface like a heated drum, a foil or a heated endless process belt.
  • the temperature is further increased to above the melting point of material C, or above the melting point of one ore more of the other materials in the mixture to make the powder stick together.
  • the dried and heated plate like sheet is fed to a calander or calander like apparatus, a belt calander, or a double belt press Between the drums, or between the belts the porous plate like sheet is densified to the required level of porosity
  • a porosity level of the intermediate between 0% and 90% is preferred If a belt calander or a double belt press is used the material can be kept under pressure for a certain time above the melting temperature of material C, attaining improved mechanical properties and less porosity
  • the plate like mate ⁇ al produced according to the process still contains some voids These voids have a negative influence on mechanical properties and electrical and thermal conductivity of the intermediate product, but surprisingly have no negative effect on the pressed end product
  • the material is an intermediate product for the production of articles like electrode plates and plates of heat exchangers In this forming process the intermediate material is heated to a temperature above the melting temperature of material C, placed in a compression mold and pressed In this process the mold temperature is below the melting point of material C
  • the processes according to the invention and the material implicad according the invention have advantages over the state of the art technologies and materials
  • Low cost basics raw mate ⁇ als are used like polymer powders
  • the polymer powders (mate ⁇ al C) are preferably produced (polyme ⁇ zed) as powder by emulsion or suspension polymerization
  • the conducting powder (material A) is preferably course synthetic graphite Mate ⁇ al C is preferably an ultra fine conducing graphite or carbon black produced from low cost heavy oil fractions Mixing is performed below the melting temperature to keep easy material flow and avoiding unwanted orientation in the material Because unwanted orientation is avoided, the end product, like a bi-polar plate is more dimensional stable than material produced according to known processes
  • Applications of thermoplastic binders make the material reusable According to the invention shaped parts can be pulverized and the obtained powder can be processed by the processing method of the invention is if it was the original powder mixture of materials A, B and C
  • a stirred vessel was filled with, 30 kg de mineralized water, 10 kg elect ⁇ cally conductive graphite with an average particle size of 150 micron, 0,5 kg carbon black, and 4 kg PVDF powder with a average particle size of 100 micron
  • the mate ⁇ al was mixed with a high shear mixer type Ultra Turax at 20 000 rpm
  • This paste (figure 1 , iteml) was casted on the protruding lower belt of a double belt press of figure 1 and spread uniformly by a doctor blade (2)
  • the water was evaporated in the drying zone (3) were the temperature was increased to 180° C
  • the dried material was fed trough the heated double belt press were it was heated up to 300°C at a pressure of 2 000 000 Pa and cooled to 100°C in the last section of the double belt press
  • Total residence time in the double belt press at 300°C was two minutes Obtained was a sheet like conductive composite material (4)

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Fuel Cell (AREA)
  • Inert Electrodes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

The invention is related to a method for the production of sheet like material that can be used in applications where polymer based material has to conduct electric current at low impedance, especially for application in electrodes, like the electrodes of polymer electrolyte membrane (PEM) fuel cells, the sheet material being electrically conductive composite material comprising a non conductive polymer binder and electrically conductive compounds. The method according to this invention has as its objective to provide a method for large-scale production of electrical conductive sheet like material in which the disadvantages of the prior art are avoided.

Description

Method for the production of conductive composite material
The invention is related to a method for the production of sheet like material that can be used in applications were polymer based material has to conduct electric current at low impedance especially for application in electrodes like the electrodes of polymer electrolyte membrane (PEM) fuel cells the sheet material being electrically conductive composite material comprising a non conductive polymer binder and electrically conductive compounds
Fuel cells are known since the discovery of Sir William Grove in the 19th century Several types of fuel cells have been developed since One of these fuel cell types is the PEM fuel cell A PEM fuel cell is comprises typically a proton conducting membrane with a catalyst-containing electrode on both sides Such an assembly is called a MEA (membrane electrode assembly) Typically these MEA s ar placed between electrically conducting plates often called bi-polar plates to form a single fuel cell, or if more of these cells are stacked such a assembly is called a fuel cell stack The mam functions of the bi-polar plates are conduction of electπcal current from one electrode to another electrode of a in series connected fuel cell distribution of hydrogen and oxygen or an oxygen containing gas, removal of reaction water sealing between the gas channels and the atmosphere Known bi-polar or mono poar plates are made from metal like stainless steel coated metal like gold-coated stainless steel, metal foam, synthetic graphite and conductive composite material Al these mateπals have their specific advantages and drawbacks as publicly known from several patents and many publications in the open literature Application of conductive composite material compπsing non-conductive polymer binders, and electrically conductive powders for application in electro chemical cells is for example known from US 4214969 However no economically feasible production method is described
A method for the production of electπcal conducive composite material for application in electrochemical cells, like fuel cells is disclosed in DE 1995019542721 According to this method a solid with good thermal conductivity and a polymer melt is mixed homogeneously Subsequently this powder is extruded to a tube like intermediate product This intermediate is according to the invention cut open and pressed flat to form a flat sheet like mateπal Application of the process according to DE 1995019542721 yields a product with a high content of conducting solid however this method has some serious drawbacks Homogeneous mixing of the polymer melt and the conductive solid is difficult if a high solid content is essential In addition to that the subsequent cooling and grinding is expensive An other drawback of the method of DE 1995019542721 is orientation during extrusion leading to non-isotropic material properties and a direction dependent coefficient of thermal expansion Not only the mechanical properties are affected, but also the electrical property like the conductivity perpendicular to the flow direction is usually reduced
The method according to this invention has as its objective to provide a method for large-scale production of electrical conductive sheet like material in which in which the disadvantages of the prior art are avoided The process starts with powdered raw mateπals A mixture is made comprising electπcal conductive powder (material A) particles with a size of 10-300 micron, a second conductive powder (material B) has elementary particles of less than 1 micron, typically 0,2 micron, and the non-conductive polymer powder (material C) has a particle size between 0,1 and 500 micron Besides materials A, B and C, the mixture can also contain non conductive fibers, conductive fibers, whiskers, hydrophobing additives, additives for hydrophilisation, and other additives that improve process ability and or material properties The polymer can be a thermoplastic polymer, a thermosetting polymer or an elastomer Suitable conductive fillers are metal powders, metal fibers, graphite, graphite fibers, carbon fibers, electrical conductive oxide powders like fluorine doped Tin oxide and Aluminum doped zinc oxide or powders coated with a conductive layer and carbon blacks Suitable thermoplastic polymers are fluoπnated polymers like PTFE, PVDF, PVF, PFA, FEP, THV, poly olefins like LD-PE, HD-PE, UHMWPE, PP, high temperature thermoplastics like PEN, PPS, PEI, PEEK The powders are preferably mixed below the melting point of mateπal C A low viscous liquid like water is mixed with the powder mixture to form a homogeneous pate like compound This low viscous liquid can be water, a appropriate organic solvent or water solvent mixtures According to an embodiment of this invention the paste like compound is applied to a heated or heatable surface like a heated drum or a heated endless process belt The paste is dried at an increased temperature that is preferably at the same temperature level as the boiling point of the low viscous liquid After evaporation of the low viscous liquid, the temperature is further increased to above the melting point of material C, or above the melting point of one ore more of the other mateπals in the mixture to make the powder stick together The dried and heated plate like sheet is fed to a calander or calander like apparatus, a belt calander, or a double belt press Between the drums, or between the belts the porous plate like sheet is densified to the required level of porosity This porosity level is preferably kept between 0% and 50%. If a belt calander or a double belt press is used the material can be kept under pressure for a certain time above the melting temperature of material C, attaining improved mechanical properties and less porosity. The plate like material produced according to the process still contains some voids or porosity. These voids could have a negative influence on mechanical properties and electrical and thermal conductivity. Surprisingly it was found that the process ability of the porous intermediate product is better than an intermediate with identical composition but no porosity. The material is an intermediate product for the production of articles like electrode plates and plates of heat exchangers. In this forming process the intermediate material is heated to a temperature above the melting temperature of material C, placed in a compression mold and pressed. In this process the mold temperature is below the melting point of material C. In another embodiment of the invention also process starts also with powdered raw materials. The electrical conductive powder (material A) particles with a size of 10- 300 micron, a second conductive powder (material B) has elementary particles of less than 1 micron, typically 0,2 micron, and the non-conductive polymer powder (material C) has a particle size between 0,1 and 500 micron. Besides materials A, B and C, the mixture can also contain non conductive fibers, conductive fibers, whiskers, hydrophobing additives, additives for hydrophilisation, and other additives that improve procesability and or material properties. The polymer can be a thermoplastic polymer, a thermosetting polymer or an elastomer. Suitable conductive fillers are metal powders, metal fibers, graphite, graphite fibers, carbon fibers, electrical conductive oxide powders like fluorine doped Tin oxide and Aluminum doped zinc oxide, powders that are coated with a conductive layer and carbon blacks. Suitable thermoplastic polymers are fluor polymers like PTFE, PVDF, PVF, PFA, FEP, THV, poly olefins like LD-PE, HD-PE, UHMWPE, PP, high temperature thermoplastics like PEN, PPS, PEI, PEEK.
The powders are preferably mixed below the melting point of material C. Optionally after a homogeneous mixture has been obtained, the powder mixture is heated to a temperature just above the melting temperature of material C to cause some agglomeration, and thus avoiding demixing.
According to an embodiment of this invention the powder mixture or the stabilized, agglomerated powder mixture is applied to a heated or heatable surface like a heated drum, a foil or a heated endless process belt. The temperature is further increased to above the melting point of material C, or above the melting point of one ore more of the other materials in the mixture to make the powder stick together. The dried and heated plate like sheet is fed to a calander or calander like apparatus, a belt calander, or a double belt press Between the drums, or between the belts the porous plate like sheet is densified to the required level of porosity A porosity level of the intermediate between 0% and 90% is preferred If a belt calander or a double belt press is used the material can be kept under pressure for a certain time above the melting temperature of material C, attaining improved mechanical properties and less porosity The plate like mateπal produced according to the process still contains some voids These voids have a negative influence on mechanical properties and electrical and thermal conductivity of the intermediate product, but surprisingly have no negative effect on the pressed end product The material is an intermediate product for the production of articles like electrode plates and plates of heat exchangers In this forming process the intermediate material is heated to a temperature above the melting temperature of material C, placed in a compression mold and pressed In this process the mold temperature is below the melting point of material C
The processes according to the invention and the material prodused according the invention have advantages over the state of the art technologies and materials Low cost basics raw mateπals are used like polymer powders The polymer powders (mateπal C) are preferably produced (polymeπzed) as powder by emulsion or suspension polymerization The conducting powder (material A) is preferably course synthetic graphite Mateπal C is preferably an ultra fine conducing graphite or carbon black produced from low cost heavy oil fractions Mixing is performed below the melting temperature to keep easy material flow and avoiding unwanted orientation in the material Because unwanted orientation is avoided, the end product, like a bi-polar plate is more dimensional stable than material produced according to known processes Applications of thermoplastic binders make the material reusable According to the invention shaped parts can be pulverized and the obtained powder can be processed by the processing method of the invention is if it was the original powder mixture of materials A, B and C
EXAMPLE 1
A stirred vessel was filled with, 30 kg de mineralized water, 10 kg electπcally conductive graphite with an average particle size of 150 micron, 0,5 kg carbon black, and 4 kg PVDF powder with a average particle size of 100 micron The mateπal was mixed with a high shear mixer type Ultra Turax at 20 000 rpm
This paste (figure 1 , iteml) was casted on the protruding lower belt of a double belt press of figure 1 and spread uniformly by a doctor blade (2) The water was evaporated in the drying zone (3) were the temperature was increased to 180° C The dried material was fed trough the heated double belt press were it was heated up to 300°C at a pressure of 2 000 000 Pa and cooled to 100°C in the last section of the double belt press Total residence time in the double belt press at 300°C was two minutes Obtained was a sheet like conductive composite material (4)

Claims

WHAT IS CLAIMED IS
1 A method for the production of an electrical conductive intermediate product comprising electπcal conductive solids, and a non conductive polymer binder wherein the intermediate material is produced by means of a continuous pressing machine
2 A method according to claim 1 wherein the raw materials are mixed and homogenized as powders to form a powder mixture
3 A method according to claim 1or 2 wherein the continuous pressing machine is an isobaπc double belt press
4 A method according to claim 1or 2 wherein the continuous pressing machine is an isochoπc double belt press
5 A method according to any of the preceding claims wherein the non conductive polymer is a fluorine containing polymer like PTFE, PVDF, PVF, PFA, FEP or THV
6 A method according to claim 5 wherein the preferred fluoπnated polymer
7 A method according to any of the preceding claims wherein the non conductive polymer is a poly olefin like LD-PE, HD-PE, UHMWPE, PP, 8 A method according to claim 5 wherein the preferred olefin polymer is HD-
PE
9 A method according to any of the preceding claims wherein the sheet like intermediate product has porosity between 0 and 90%
10 A method according to any of the preceding claims wherein the intermediate product is reinforced with fibers like glass fibers, metal fibers, carbon fibers, graphite fibers or aramid fibers
11 A method according to any of the preceding claims wherein the intermediate product is used for the production of shaped parts like electrodes or fuel cell plates or the conductive part of fuel cell plates 12 A method according to any of the preceding claims wherein shaped parts of conductive composite material are pulverized and this powder is used for the production of the conductive intermediate product
13 A method according to any of the preceding claims wherein the production process contains, mixing of powder like raw materials with or without an low viscous liquid, distribution of the powder mixture or paste on an foil like carrier, a endless process belt or a drum, optionally drying, heating to a temperature above the melting point, or if there is no melting point above the Tg of de non conductive polymer, forming to a sheet like material by rolling or pressing, and cooling to a temperature below the melting point or the Tg of the non conducting polymer
14 A method of forming shaped parts wherein the process compπses the following steps,
• Cutting the intermediate product to the right size, weight or volume to prepare a pre-form
• Heating of the preform to a temperature above Tm if semi crystalline polymer is used or above Tg if amorphous polymer is used • Placing the heated perform in a suitable mold in a suitable pressing machine like a hydraulic press, the mold having a temperature below Tg or Tm of the polymer and preferably avoiding direct contact between the mold surface and the heated preform prior to closing of the mold
• Closing of the mold at high pressure to form the perform to a negative of the mold halves
• Release from the mold
PCT/NL2001/000137 2000-02-17 2001-02-19 Method for the production of conductive composite material Ceased WO2001060593A2 (en)

Priority Applications (2)

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EP01910243A EP1299225A2 (en) 2000-02-17 2001-02-19 Method for the production of conductive composite material
JP2001559673A JP2003523066A (en) 2000-02-17 2001-02-19 Method for producing conductive composite material

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NL1014403A NL1014403C1 (en) 2000-02-17 2000-02-17 Method for manufacturing a plate-shaped semi-finished product that is suitable for use in, among others, Polymer Electrolyte Fuel Cells.
NL1014403 2000-02-17

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DE102020006943A1 (en) 2020-11-12 2022-05-12 Cellcentric Gmbh & Co. Kg Manufacturing process for components of a fuel cell stack
WO2022101351A2 (en) 2020-11-12 2022-05-19 Cellcentric Gmbh & Co. Kg Method of production for components of a fuel cell stack
US12564988B2 (en) 2020-11-12 2026-03-03 Cellcentric Gmbh & Co. Kg Method of production for components of a fuel cell stack

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JP2003523066A (en) 2003-07-29
NL1014403C1 (en) 2001-08-20
WO2001060593A3 (en) 2002-08-15
US20030160352A1 (en) 2003-08-28
EP1299225A2 (en) 2003-04-09

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