WO2022150953A1 - Plaque bipolaire et son procédé de fabrication, et pile à combustible à membrane échangeuse de protons - Google Patents

Plaque bipolaire et son procédé de fabrication, et pile à combustible à membrane échangeuse de protons Download PDF

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Publication number
WO2022150953A1
WO2022150953A1 PCT/CN2021/071215 CN2021071215W WO2022150953A1 WO 2022150953 A1 WO2022150953 A1 WO 2022150953A1 CN 2021071215 W CN2021071215 W CN 2021071215W WO 2022150953 A1 WO2022150953 A1 WO 2022150953A1
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WO
WIPO (PCT)
Prior art keywords
bipolar plate
layer
base layer
filler
base
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PCT/CN2021/071215
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English (en)
Chinese (zh)
Inventor
韦剑飞
聂骁
霍夫曼·洛塔尔
库尔茨贝克·施特凡
Original Assignee
舍弗勒技术股份两合公司
韦剑飞
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Application filed by 舍弗勒技术股份两合公司, 韦剑飞 filed Critical 舍弗勒技术股份两合公司
Priority to PCT/CN2021/071215 priority Critical patent/WO2022150953A1/fr
Publication of WO2022150953A1 publication Critical patent/WO2022150953A1/fr

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    • 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
    • H01M8/0228—Composites in the form of layered or coated products

Definitions

  • the present invention relates to the field of fuel cells, and more particularly, to a bipolar plate for a fuel cell and a method for manufacturing the same, and a proton exchange membrane fuel cell including the bipolar plate.
  • Bipolar plates typically serve the following functions: distribute hydrogen and air within the cell; separate individual cells in the stack; support water management within the cell; serve as a conductive path from the cell to the load; and support the thermal management of the cell (cooling and heating). Therefore, first of all, the bipolar plate needs to have good electrical and thermal conductivity, good processing and forming ability, and certain hydrophobic properties; secondly, since the bipolar plate works under acidic conditions, the bipolar plate should also have corrosion resistance; again; , in order to increase the energy density, the bipolar plate should be as thin as possible.
  • Different materials are used to manufacture bipolar plates in the prior art, as follows.
  • the first material is various graphite materials.
  • Graphite materials have good durability, but bipolar plates made of graphite materials are difficult to make sufficiently thin due to their poor mechanical properties (low strength and poor toughness).
  • the second material is a metallic material. Due to the good mechanical properties of metal materials, bipolar plates made of metal materials can be very thin, and metal materials such as stainless steel can have good cold deformation forming properties, which are suitable for rapid production in large quantities. However, with the exception of noble metals such as gold, platinum, iridium, etc., the corrosion resistance of other metals is insufficient. Although stainless steel has good corrosion resistance, its corrosion resistance is due to the formation of a high chromium oxide film on the surface. The conductivity of the oxide film is low, and the contact resistance between the bipolar plate and the gas diffusion layer (GDL) increases. The resistance loss of the fuel cell increases. In order to improve corrosion resistance while maintaining good surface conductivity, a coating with good corrosion resistance is usually formed on the surface of metal materials.
  • GDL gas diffusion layer
  • the surface coating increases the cost of the bipolar plate, and if the coating is not completely dense, the base metal ions may contaminate the membrane electrode of the fuel cell during use, thereby deteriorating the performance of the fuel cell.
  • the durability is often not comparable to that of bipolar plates made of graphite materials.
  • the third material is a composite material.
  • Composite materials are mixtures of base polymers with electrically and thermally conductive fillers (eg, graphite, carbon nanotubes, etc.). Although the corrosion resistance is improved compared to bipolar plates made of metallic materials, the electrical and thermal conductivity of composites is a bottleneck limiting their use due to the presence of non-conductive or low-conductivity polymer phases.
  • the electrical and thermal conductivity of composite materials depends on the volume percentage concentration of electrical and thermal conductive fillers. A high volume percentage concentration of electrical and thermal conductive fillers can increase electrical and thermal conductivity, but at the same time, mechanical properties decrease. Therefore, how to solve the electrical and thermal conductivity of composite materials while maintaining Sufficient mechanical strength is one of the keys to composite bipolar plates.
  • An object of the present invention is to provide a new bipolar plate and a method for manufacturing the same, which has better durability and can be made thin enough.
  • Another object of the present invention is to provide a proton exchange membrane fuel cell including the above bipolar plate.
  • the present invention provides a bipolar plate for use in a fuel cell and comprising:
  • a base layer made of a metallic material
  • a filler layer, the filler layer is made of a composite material mixed with a base polymer and a conductive filler, and the filler layer is fixed to the base layer in a manner of covering one side or both sides of the base layer.
  • the volume percentage concentration of the conductive filler is more than 70%.
  • the base polymer comprises at least one selected from the following thermoplastic materials: PP, PVF, PVDF, PTFE, PCTFE, ETFE, PA, PPA, PPS, LCP, PEK, PEEK, PC, PPE, PSU , PESU, PEI; or
  • the base polymer includes at least one selected from the following thermosetting materials: phenolic resin, epoxy resin, melamine resin, polyimide, unsaturated polyester resin, polyamideimide; or
  • the base polymer includes at least one selected from the following rubbers: FKM, FFKM, EPDM, HNBR, CR, IIR, CSM, FVMQ.
  • the conductive filler is at least one selected from the following materials: carbon black, graphite, carbon fiber, carbon nanotube, graphene, ceramic and metal particles.
  • the thickness D1 of the base layer and the thickness D2 of the filler layer satisfy the following relationship: 20 ⁇ m ⁇ D1, and 1 ⁇ m ⁇ D2 ⁇ 100 ⁇ m.
  • the base layer is a metal plate or a metal mesh, and the elongation of the metal material is greater than 20%.
  • the metal material is at least one selected from the following materials: low carbon steel, stainless steel, copper, copper alloy, aluminum, aluminum alloy.
  • the surface of the base layer is subjected to anti-corrosion treatment and/or roughening treatment.
  • the present invention also provides a method for manufacturing a bipolar plate according to any one of the above technical solutions, the manufacturing method comprising the following steps:
  • the filler layer is fixed to the base layer in a manner of covering one side or both sides of the base layer to form a semi-finished product
  • the semi-finished product is formed into a bipolar plate having a predetermined geometry.
  • the base polymer is formed into a powder state or a liquid state.
  • the base polymer and the conductive material are mixed or mixed with a ball mill to obtain the composite material.
  • the present invention also provides the following proton exchange membrane fuel cell, which includes the bipolar plate described in any one of the above technical solutions.
  • the present invention provides a bipolar plate and a manufacturing method thereof.
  • the bipolar plate includes a base layer and a filler layer fixed together, the base layer is made of a metal material, and the filler layer is made of a mixed material of a base polymer and a conductive filler.
  • the filler layer is fixed to the base layer in a manner of covering one side or both sides of the base layer.
  • the bipolar plate uses the base layer made of metal material as the skeleton, the machinability and structural strength of the entire bipolar plate are improved, so that the entire bipolar plate can be made thin enough; in addition, the bipolar plate It also includes a filler layer made of a composite material obtained by mixing the base polymer and the conductive filler, and the filler layer has strong corrosion resistance, so that the durability of the entire bipolar plate is effectively improved.
  • FIG. 1 is a schematic diagram showing the structure of a bipolar plate according to a first embodiment of the present invention.
  • FIG. 2 is a schematic diagram showing a partial structure of a rolling device for manufacturing the semi-finished product of the bipolar plate shown in FIG. 1 .
  • FIG. 3 is a schematic diagram showing the structure of a bipolar plate according to a second embodiment of the present invention.
  • the bipolar plate according to the present invention can be used in a fuel cell, and the function of the bipolar plate in the fuel cell is the same as that of the conventional bipolar plate described in the background art. Exemplary embodiments of the present invention are described below with reference to the accompanying drawings.
  • the bipolar plate according to the first embodiment of the present invention includes a base layer 1 and two filler layers 2 fixed together.
  • the base layer 1 is a metal plate made of a metal material and is located between the two filler layers 2 , so that the base layer 1 and the two filler layers 2 are stacked together in the thickness direction T.
  • the thickness D1 of the base layer 1 was 50 ⁇ m. In this way, the base layer 1 can be made thin enough by taking advantage of the excellent machinability of metal; and when the bipolar plate is made very thin, the base layer 1 can enhance the strength of the bipolar plate and play the role of a skeleton .
  • the metal material for making the base layer 1 may be at least one material selected from the following materials: low carbon steel, stainless steel, copper, copper alloy, aluminum, aluminum alloy. In the case of low carbon steel, the low carbon steel is preferably treated for corrosion resistance.
  • the metal plate is roughened. Concavities and convexities or textures can be formed on the surface of the metal plate by rolling, and the surface of the metal plate can also be roughened by chemical treatment or sandblasting, or by laser roughening or texturing.
  • the filler layer 2 is made of a composite material made by mixing a base polymer and a conductive filler, the base polymer is used to bond various substances in the composite material together, and the conductive filler is used to realize the Conductive function.
  • the two layers of filler layers 2 sandwich the base layer 1 , and each filler layer 2 is attached and fixed to the base layer 1 in a manner of covering the corresponding side surfaces of the base layer 1 .
  • the filler layer 2 can be made to have a sufficient thickness.
  • the filler layer 2 The thickness D2 is 20 ⁇ m.
  • the filler layer 2 mainly serves the purpose of improving the durability of the bipolar plate.
  • the above-mentioned base polymer is preferably selected from a material with very good acid resistance.
  • the base polymer may include at least one selected from the following thermoplastic materials: PP (polypropylene), PVF (polyvinyl fluoride), PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PCTFE ( Polychlorotrifluoroethylene), ETFE (ethylene tetrafluoroethylene), PA (polyamide), PPA (polyphthalamide), PPS (polyphenylene sulfide), LCP (liquid crystal polymer), PEK (polyether) ether ketone), PEEK (polyether ether ketone), PC (polycarbonate), PPE (polyphenylene ether), PSU (polysulfone), PESU (polyethersulfone), PEI (
  • the base polymer After selecting the base polymer and the conductive material, before uniformly mixing the base polymer and the conductive filler to obtain the composite material, the base polymer is formed into a fine powder state or a low viscosity liquid state with a viscosity less than a predetermined value, the fine powder state and The low viscosity liquid state promotes uniform mixing between the base polymer and the conductive filler.
  • ball milling, stirring or other efficient mixing methods can be used to uniformly mix the base polymer and the conductive material together, thereby utilizing The base polymer and conductive filler result in a well-mixed composite.
  • the volume percentage concentration of the conductive filler is 70%.
  • the bipolar plate according to the first embodiment of the present invention has both the advantages of the bipolar plate made only of the metal material and the bipolar plate made only of the composite material, and can improve the durability while making it thin enough.
  • the manufacturing method includes the following steps.
  • the metal plate as the base layer 1 is made of the metal material; and the base polymer and the conductive filler are respectively selected according to the needs, so that the base polymer and the conductive filler are in a predetermined volume percentage concentration (for example, the volume of the conductive filler).
  • the percentage concentration is 70%) uniformly mixed to obtain a composite material, and the filler layer 2 is formed by using the composite material.
  • the two layers of filler layers 2 and the base layer 1 are rolled by the rolling device as shown in FIG.
  • the processing temperature and the temperature of each rolling roll can be determined according to the type of the base polymer, and specifically, the temperature can be controlled by heating or cooling the rolls during the rolling process.
  • a large number of semi-finished products of bipolar plates can be continuously processed, which is beneficial to large-scale industrial production.
  • the semi-finished product is formed into a finished bipolar plate having a predetermined geometric shape, and the above-mentioned geometric shape can be determined in consideration of the structure and size of the fuel cell to which the bipolar plate is applied.
  • the structure of the bipolar plate according to the second embodiment of the present invention is different from that of the bipolar plate according to the first embodiment of the present invention.
  • the base layer 1 is a metal mesh made of a metal material
  • the bipolar plate includes only one filler layer 2 , and the filler layer 2 is attached and fixed to one side of the base layer 1 , so that the base layer 1 and the filler layer 2 are stacked together in the thickness direction T.
  • the metal mesh As the base layer 1, since the metal mesh has sufficient adhesion, it is not necessary to roughen the metal mesh. In order to prevent the side of the metal mesh not attached with the filler layer 2 from being corroded in contact with a coolant (such as water), etc., thereby affecting the durability of the entire bipolar plate, it is preferable to use a corrosion-resistant metal material to make the metal mesh, or to make the metal mesh The mesh is treated for corrosion resistance.
  • the bipolar plate according to the second embodiment of the present invention can be formed using a similar manufacturing method to the bipolar plate according to the first embodiment of the present invention, and has the same characteristics as the first embodiment. Effect.
  • the present invention also provides a proton exchange membrane fuel cell, which adopts the bipolar plate with the above structure.
  • the thickness of the bipolar plate including the base layer 1 can be sufficiently thin. It should be understood that D1>200 ⁇ m can also be made if required.
  • the thickness D2 of the filler layer 2 satisfies the following relationship: 1 ⁇ m ⁇ D2 ⁇ 100 ⁇ m, so that the thickness of the bipolar plate including the filler layer 2 can be made thin enough to prevent pinholes in the filler layer 2 from causing damage to the base layer 1 . Undesirable corrosion occurs. D2>100 ⁇ m can also be made if required.
  • volume percentage concentration of the conductive filler in the filler layer 2 is described as 70% in the above specific embodiment, the present invention is not limited to this. As long as the volume percentage concentration of the conductive filler in the filler layer 2 is greater than or equal to 70%, the filler layer 2 can have better conductivity. Further preferably, in the filler layer 2, the volume percentage concentration of the conductive filler is greater than or equal to 80%.
  • bipolar plates according to the present invention are described in the above specific embodiments for use in proton exchange membrane fuel cells, it should be understood that the bipolar plates according to the present invention can also be used in other fuel cells.

Abstract

L'invention concerne une plaque bipolaire, comprenant : une couche de base (1) constituée d'un matériau métallique; et une couche de charge (2) constituée d'un matériau composite formé par mélange d'un polymère de base et d'une charge conductrice, la couche de charge (2) étant fixée à la couche de base (1) de manière à s'étendre sur une surface latérale ou deux surfaces latérales de la couche de base (1). De cette manière, les performances d'usinage et la résistance structurale de la plaque bipolaire entière sont améliorées, de telle sorte que toute la plaque bipolaire peut être fabriquée pour être suffisamment mince, et la durabilité de la plaque bipolaire entière est efficacement améliorée. L'invention concerne également un procédé de fabrication de la plaque bipolaire et une pile à combustible à membrane échangeuse de protons comprenant la plaque bipolaire.
PCT/CN2021/071215 2021-01-12 2021-01-12 Plaque bipolaire et son procédé de fabrication, et pile à combustible à membrane échangeuse de protons WO2022150953A1 (fr)

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PCT/CN2021/071215 WO2022150953A1 (fr) 2021-01-12 2021-01-12 Plaque bipolaire et son procédé de fabrication, et pile à combustible à membrane échangeuse de protons

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PCT/CN2021/071215 WO2022150953A1 (fr) 2021-01-12 2021-01-12 Plaque bipolaire et son procédé de fabrication, et pile à combustible à membrane échangeuse de protons

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020001743A1 (en) * 2000-02-08 2002-01-03 Davis John Herbert Composite bipolar plate separator structrues for polymer electrolyte membrane (PEM) electrochemical and fuel cells
US6372376B1 (en) * 1999-12-07 2002-04-16 General Motors Corporation Corrosion resistant PEM fuel cell
JP2002216786A (ja) * 2001-01-23 2002-08-02 Hitachi Ltd 固体高分子型燃料電池
US20040058249A1 (en) * 2002-09-25 2004-03-25 Yuqi Cai Mesh reinforced fuel cell separator plate
JP2006164658A (ja) * 2004-12-06 2006-06-22 Mitsubishi Plastics Ind Ltd 燃料電池用構造体
WO2007049765A1 (fr) * 2005-10-27 2007-05-03 Mitsubishi Plastics, Inc. Separateur pour pile a combustible, pile a combustible l’utilisant et composition de peinture pour preparer le separateur
CN101911355A (zh) * 2008-01-21 2010-12-08 现代Hysco株式会社 燃料电池用金属隔板及其制造方法
JP2017071218A (ja) * 2015-10-05 2017-04-13 新日鉄住金マテリアルズ株式会社 ステンレス鋼板カーボン複合材及びその製造方法
JP2017188255A (ja) * 2016-04-04 2017-10-12 新日鉄住金マテリアルズ株式会社 燃料電池用セパレータおよびその製造方法
CN109390606A (zh) * 2017-08-04 2019-02-26 丰田自动车株式会社 用于燃料电池的分离器、燃料电池及其分离器的制造方法
WO2019194112A1 (fr) * 2018-04-02 2019-10-10 日鉄ケミカル＆マテリアル株式会社 Précurseur de stratifié métal-carbone et son procédé de fabrication

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6372376B1 (en) * 1999-12-07 2002-04-16 General Motors Corporation Corrosion resistant PEM fuel cell
US20020001743A1 (en) * 2000-02-08 2002-01-03 Davis John Herbert Composite bipolar plate separator structrues for polymer electrolyte membrane (PEM) electrochemical and fuel cells
JP2002216786A (ja) * 2001-01-23 2002-08-02 Hitachi Ltd 固体高分子型燃料電池
US20040058249A1 (en) * 2002-09-25 2004-03-25 Yuqi Cai Mesh reinforced fuel cell separator plate
JP2006164658A (ja) * 2004-12-06 2006-06-22 Mitsubishi Plastics Ind Ltd 燃料電池用構造体
WO2007049765A1 (fr) * 2005-10-27 2007-05-03 Mitsubishi Plastics, Inc. Separateur pour pile a combustible, pile a combustible l’utilisant et composition de peinture pour preparer le separateur
CN101911355A (zh) * 2008-01-21 2010-12-08 现代Hysco株式会社 燃料电池用金属隔板及其制造方法
JP2017071218A (ja) * 2015-10-05 2017-04-13 新日鉄住金マテリアルズ株式会社 ステンレス鋼板カーボン複合材及びその製造方法
JP2017188255A (ja) * 2016-04-04 2017-10-12 新日鉄住金マテリアルズ株式会社 燃料電池用セパレータおよびその製造方法
CN109390606A (zh) * 2017-08-04 2019-02-26 丰田自动车株式会社 用于燃料电池的分离器、燃料电池及其分离器的制造方法
WO2019194112A1 (fr) * 2018-04-02 2019-10-10 日鉄ケミカル＆マテリアル株式会社 Précurseur de stratifié métal-carbone et son procédé de fabrication

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