WO2023240227A1 - Plaque bipolaire en graphite pour piles à combustible fabriquées à l'aide d'un thermoplastique liquide recyclable - Google Patents

Plaque bipolaire en graphite pour piles à combustible fabriquées à l'aide d'un thermoplastique liquide recyclable Download PDF

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Publication number
WO2023240227A1
WO2023240227A1 PCT/US2023/068189 US2023068189W WO2023240227A1 WO 2023240227 A1 WO2023240227 A1 WO 2023240227A1 US 2023068189 W US2023068189 W US 2023068189W WO 2023240227 A1 WO2023240227 A1 WO 2023240227A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphite
bipolar plate
thermoplastic
viscosity
mold
Prior art date
Application number
PCT/US2023/068189
Other languages
English (en)
Inventor
Parvinder Walia
Ranjit PACHHA
Original Assignee
Magna Exteriors Inc.
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 Magna Exteriors Inc. filed Critical Magna Exteriors Inc.
Publication of WO2023240227A1 publication Critical patent/WO2023240227A1/fr

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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0221—Organic resins; Organic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • 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
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/008—Disposal or recycling of fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0213—Gas-impermeable carbon-containing materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0226—Composites in the form of mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0255—Specific separating techniques using different melting or softening temperatures of the materials to be separated
    • 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
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0013—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fillers dispersed in the moulding material, e.g. metal particles
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • 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
    • B29K2233/00—Use of polymers of unsaturated acids or derivatives thereof, as reinforcement
    • B29K2233/04—Polymers of esters
    • B29K2233/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • 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
    • B29K2507/00—Use of elements other than metals as filler
    • B29K2507/04—Carbon

Definitions

  • the present invention relates to a graphite bipolar plate for fuel cells such as proposed for use in vehicles.
  • Bipolar plates used in fuel cells typically are about 80% of the weight and 40% of the cost of a typical fuel cell. Therefore, technology in the manufacturing and improving bipolar plates has rapidly advanced.
  • Bipolar plates are made of several materials such as stainless steel, thermoset or thermoplastics containing graphite.
  • Stainless steel bipolar plates are prone to corrosion and require expensive coatings to achieve a desired life cycle of 8000 hrs.
  • Graphite thermoset materials are not recyclable when they have reached the end of life cycle of the fuel cell.
  • Typical thermoplastic material like polypropylene, polyamide or polycarbonate are solid at ambient temperature and hence cannot accommodate a high amount of graphite.
  • Lower graphite content thermoplastic ends up with lower conductivity and hence limited application in bipolar plates. In vehicle manufacturing it is desirable to provide recyclable materials and with vehicles, including fuel cells, this goal remains. Because a fuel cell is such a large part of a vehicle a recyclable material fuel cell is highly desirable.
  • bipolar plates have poor performance due to lower conductivity.
  • the solid thermoplastic resin can only accommodate low amount of graphite and hence lower conductivity. If higher graphite is added to normal solid thermoplastic injection molded resins then it becomes difficult to injection mold the material. Additionally, the final bipolar plates made with this high graphite content are brittle in nature and have poor structural integrity than it required for automotive fuel cells. Additionally, while attempts have been made, attempting to get high enough content of conductive materials into a moldable thermoplastic that will allow a precision molded bipolar plate which must include flow paths and cooling channels has not been successful.
  • thermoplastic bipolar plate for a fuel cell formed by compression molding a thickened low viscosity (meth)acrylate resin which hereby will be called liquid thermoplastic resin and having from about 60% to about 85% graphite by volume.
  • thermoplastic graphite filled bipolar plate including at least one cooling channel and at least one flow path comprising the steps of:
  • step B Adding at least a catalyst to the composition of step A for crosslinking the thermoplastic liquid resin;
  • Liquid thermoplastic resin that can be thickened and converted to bulk molding compound
  • thermoplastic resin which can accommodate high graphite loading and hence high electrical conductivity
  • thermoplastic resin once cured can be recycled on heating; 5.
  • Compression molding BMC consisting of liquid (meth)acrylate resin and high concentration graphite into graphite bipolar plate;
  • thermoplastic (meth)acrylate resin that is thickened to make bulk molding compound for graphite bipolar plate
  • Thickened bulk molding compound when compression molded provides uniform distribution of the components to produce graphite bipolar plate with good mechanical properties and electrical conductivity;
  • Recyclable graphite bipolar plate made with liquid thermoplastic (meth)acrylate resin and graphite; and,
  • Figure 1 is a schematic view of a typical fuel cell having bipolar plates
  • Figure 2 is a perspective view of a bipolar plate
  • Figure 3 is a schematic view of the process for producing a bipolar plate of the present invention.
  • a fuel cell generally shown at 10 includes bipolar plates 12 and 14.
  • Bipolar plates include at least one flow path 16 and typically at least one cooling channel 18.
  • the flow panels and cooling channels are critical for proper operation of the fuel cell and require precision forming of the bipolar plates 12 and 14 to provide proper operation of the fuel cell. Since the bipolar plates are also the anode and cathode of the fuel cell, they require high conductivity materials in their construction.
  • a graphite filled thermoplastic bipolar plate (12, 14) for a fuel cell 10 comprising a thickened low viscosity molded acrylic thermoplastic formed by injection molding and having from about 60% to about 85% graphite by volume.
  • the graphite used is typically either crystalline graphite, graphite flake, synthetic graphite, and mixtures of these. Suitable graphite materials are available from Timrex of Imerys S.A. Paris France, Asbury Carbons, Asbury New Jersey, USA. and SGL Carbon LLC Charlotte, North Carolina, USA with trade name designations, 3243, 230U, KS75, SGL02, and expanded graphite.
  • the composition may also include from about 0% to about 10% chopped carbon fiber available from Zolteck Corporation, of Bridgeton, Missouri USA under the PX35 designation. Other chopped carbon fibers can also be used.
  • the graphite filled thermoplastic plate (12, 14) is manufactured using a hardened compression moldable precursor in which the graphite is mixed in and forming a thickened acrylic thermoplastic having viscosity of greater than 1 Mcps. Accelerators and initiators are used in the composition to provide a solid thermoformable material which is highly filled with graphite. This thermoformable material is then formed into the bipolar plate which includes flow paths and cooling channels suitable for use in a fuel cell. Typically, compression molding is used and preferred for forming the bipolar plate. However, other suitable methods of forming thermoformable material may be used in the present invention.
  • the resulting bipolar plate is effective for use in a fuel cell and is recyclable at end of life of the fuel cell by separation of the thermoplastic component and the graphite component, which are both reusable for manufacture of other products.
  • thermoplastic graphite filled bipolar plate (12, 14) including at least one cooling channel 16 and at least one flow path 18 is set forth.
  • the process includes the steps of:
  • A. Providing a liquid thermoplastic including from 60% to about 85% graphite filled acrylic polymer thickened to a viscosity of greater than 1 Mcps shown in step 22.
  • B. Adding at least a catalyst to the composition of step A for crosslinking of the liquid acrylic polymer as shown at 24 and thereafter forming a thermoforming composition shown at 26.
  • thermoplastic resin 30 A. providing a liquid thermoplastic resin 30 and mixing suitable additives with the thermoplastic in a mixing vessel.
  • suitable additives such as accelerators initiators, rheological modifiers and wetting agents are included as desired as will be appreciated by those skilled in the art. .
  • the compression moldable hardened material 36 is then placed in a mold for forming a bipolar plate (12, 14) which includes at least one cooling channel 18 and flow path 16 and forming a bipolar plate.
  • chopped carbon fiber material in amounts of from about 0% to about 10% are added in step B. Additionally in the preferred embodiment the composition of step B is further allowed to mature from about 24 to about 48 hours to increase viscosity.
  • the liquid thermoplastic resin is used in combination with graphite fillers with or without fiber reinforcement to make bulk molding compound.
  • the molding compound can then be cured during the compression molding process to make bipolar plate.
  • An improvement in the process is chemical thickening of low viscosity resin to high viscosity gel after the resin is mixed with all the other components of the compound.
  • Thickening of the resin prevents the separation of the filler and fiber during the compression molding at high temperature. If the compound is not thickened, the resin, filler and the fiber separates and bipolar plate with segregated individual components are formed.
  • Bipolar plates formed in this manner will have poor continuity of electrical conductivity and poor mechanical properties.
  • the increased viscosity prevents segregation of various components of compound and promotes compositional uniformity of bipolar plate.
  • Rheological modifier is added and mixed for another 5-10 minutes.
  • This mixture is transferred to a Baker Perkin Kneader.
  • Carbon fiber if used is added to the kneader. Carbon fiber is added in amounts of 2%, 4%, 6%, 8% and 10% by weight in separate batches and are found to be suitable for molding into a bipolar plate.
  • Graphite is added to the above mixtures in amounts of 60% 65%, 70%, 75%, 80% and 85% by weight to each of the above mixtures and are found suitable for molding of the bipolar plate. After addition of the graphite the material is kneaded for 30-60 minutes.
  • the batch is water cooled during kneading to prevent the temperature raising above 30°C.
  • Material is transferred into a barrier film and allowed to mature at a temperature ranging from 30-50°C for 24 hours before molding.
  • the resulting Graphite filled compounds are allowed to mature and increase in viscosity for 24-48 hours until the viscosity of greater than 1 Mcps which is found to be suitable for molding into a puck.
  • the graphite compounds are molded into puck 36 by placing a known amount of graphite compound into a puck shaped mold 38 and pressing the graphite under pressure into the mold 38.
  • the pucks are placed into a mold with flow channels and compression molded at a mold temperature between 70-120°C pressure of 500-1300 psi cycle time 60-300 sec.
  • the pucks made from the above molding compounds are cured during compression molding process to make bipolar plates.
  • the Bipolar plates made are found to be suitable for use in fuel cells and are recyclable at their end of life.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Sustainable Energy (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Environmental & Geological Engineering (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne une plaque bipolaire thermoplastique remplie de graphite pour une pile à combustible formée par moulage par compression et comprenant un thermoplastique acrylique de faible viscosité épaissi et ayant d'environ 60 % à environ 85 % de graphite en volume. L'invention concerne également un procédé d'épaississement d'un thermoplastique liquide contenant des quantités élevées de graphite et le moulage d'une plaque bipolaire.
PCT/US2023/068189 2022-06-09 2023-06-09 Plaque bipolaire en graphite pour piles à combustible fabriquées à l'aide d'un thermoplastique liquide recyclable WO2023240227A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202263350694P 2022-06-09 2022-06-09
US63/350,694 2022-06-09

Publications (1)

Publication Number Publication Date
WO2023240227A1 true WO2023240227A1 (fr) 2023-12-14

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2023/068189 WO2023240227A1 (fr) 2022-06-09 2023-06-09 Plaque bipolaire en graphite pour piles à combustible fabriquées à l'aide d'un thermoplastique liquide recyclable

Country Status (1)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005100814A (ja) * 2003-09-25 2005-04-14 Dainippon Ink & Chem Inc 燃料電池用セパレータ及び燃料電池
EP1553651A1 (fr) * 2002-08-23 2005-07-13 Honda Giken Kogyo Kabushiki Kaisha Separateur de pile a combustible et son procede de fabrication
KR100660144B1 (ko) * 2006-03-08 2006-12-20 한국타이어 주식회사 연료전지 분리판 사출성형을 위한 열가소성 소재
US20160197360A1 (en) * 2015-01-02 2016-07-07 Hankook Tire Co., Ltd. Fuel cell separating plate and method of manufacturing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1553651A1 (fr) * 2002-08-23 2005-07-13 Honda Giken Kogyo Kabushiki Kaisha Separateur de pile a combustible et son procede de fabrication
JP2005100814A (ja) * 2003-09-25 2005-04-14 Dainippon Ink & Chem Inc 燃料電池用セパレータ及び燃料電池
KR100660144B1 (ko) * 2006-03-08 2006-12-20 한국타이어 주식회사 연료전지 분리판 사출성형을 위한 열가소성 소재
US20160197360A1 (en) * 2015-01-02 2016-07-07 Hankook Tire Co., Ltd. Fuel cell separating plate and method of manufacturing the same

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