WO2017180759A1 - Engineered low-cost, high-performance conductive composite - Google Patents

Engineered low-cost, high-performance conductive composite Download PDF

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Publication number
WO2017180759A1
WO2017180759A1 PCT/US2017/027231 US2017027231W WO2017180759A1 WO 2017180759 A1 WO2017180759 A1 WO 2017180759A1 US 2017027231 W US2017027231 W US 2017027231W WO 2017180759 A1 WO2017180759 A1 WO 2017180759A1
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Prior art keywords
powdered
bipolar plate
particle
additive
conductive
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PCT/US2017/027231
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French (fr)
Inventor
David RESTREPO
Matt McINNIS
Sean CHRISTIANSEN
Jeff Bullington
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Garmor Inc.
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Publication of WO2017180759A1 publication Critical patent/WO2017180759A1/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/24Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon

Definitions

  • the present invention relates in general to the field of low-cost, high-performance composites.
  • Bipolar plates are an important key component of fuel cells, flow batteries and electronic applications. Bipolar plates used in fuel cells are primarily used because of their ability to simultaneously provide a thermally and electrically conductive plate that also distributes and separates gases. Significant effort is aimed at reducing the weight and cost of bipolar plates for fuel cell applications. Weight and cost constraints make solving fundamental problems with bipolar plate performance. Poor chemical stability of metallic plates allows for resistive oxides to form on the plate surface, significantly reducing output electricity.
  • Today, most bipolar plates are composed entirely of graphite or mostly graphite and a polymer filler to create a lightweight composite bipolar plate. Thus far, graphite has been an ideal candidate for composing bipolar plates because of its mechanical, chemical, thermal, gas barrier, electrical, flame retardant and other properties, however it suffers from poor electrical conductivity and high cost of manufacture.
  • the method herein enables the dispersion/compounding of graphite, carbon black, graphene oxide or any additive with a polymeric component that can be extruded, stamped, or otherwise mass-produced into a bipolar plate.
  • the particles of the one material are coated with the material of another conductive component or multiple conductive components using a milling process.
  • the coated surface of the material creates conductive connective pathways through the volume of the final composite structure.
  • the present invention includes a method of making a conductive, composite bipolar plate made of coated particles for making a composite material that enhances a property of the composite material, comprising: providing a powdered component called a powdered host particle; providing a second powdered component called a conductive additive that comprises a softening or melting temperature higher than the melting point of the powdered host particle; inputting said powdered host particle and said conductive additive into a ball mill; and ball milling said powdered host and said conductive additive for a milling time to sufficiently mix but not melt the powdered host particle into a conductive host-additive particle.
  • the powdered host particle is a powder from a resin of polymethylpentene.
  • the conductive additive is comprised of graphite, graphene oxide, carbon nanotubes, or carbon nanowires.
  • the conductive host-additive particle is formed into a bipolar plate assembly for a PEM fuel cell, and the bipolar plate comprises a formable resin with one or more conductive materials.
  • the conductive host-additive particle is formed into a bipolar plate assembly for a PEM fuel cell that comprises the bipolar plate having a plurality of formed serpentine flow field on a first side of said bipolar plate and an interdigitated flow field on a second side of said bipolar plate, a plate margin having a first header aperture formed therethrough, a first port formed therethrough between said first header aperture and said serpentine flow field, a second header aperture formed therethrough, and a second port formed therethrough between said second header aperture and said interdigitated flow field.
  • the conductive host-additive particle is formed into a bipolar plate assembly for a PEM fuel cell that comprises a first seal disposed on said second side of said bipolar plate and having a first passageway formed therein to define a first fluid transmission path between said first header and a second passageway formed therein to define a second fluid transmission path between said second port and said interdigitated flow field.
  • the powdered host particle is a powder from any resin of a particle size greater than 5 ⁇ .
  • the powdered host particle is a powder from a resin of polymethylpentene.
  • the conductive additive is comprised of graphite, graphene oxide, carbon nanotubes or carbon nanowires or any combination formed in situ in the ball mill prior to the addition of the powdered host particle.
  • Another embodiment of the present invention includes a method of making a conductive composite particle or material, comprising: providing a powdered host particle; providing a conductive additive with a softening or melting temperature higher than the melting point of the powdered host particle; mixing the powdered host particle and the powdered additive in a ball mill; and milling the powdered host and the powdered additive for a time sufficient to mix but not melt the powdered host particle to form an electrically conductive host-additive blend.
  • the powdered host particle is a powder from a resin of polymethylpentene.
  • the electrically conductive host-additive blend has at least one of the following properties: a bulk density less than 1.75 g/cm 3 , an electrical conductivity greater than 250 S/cm, or a Rockwell hardness > 80.
  • the method further comprises the step of extruding, stamping, or otherwise mass-producing the electrically conductive host-additive blend into a bipolar plate.
  • the bipolar plate is adapted for use in a PEM fuel cell, wherein the bipolar plate further comprises a formable resin with one or more conductive additives.
  • the method further comprises the step of assembling the bipolar plate into a PEM fuel cell that comprises the bipolar plate having a plurality of formed serpentine flow field on a first side of said bipolar plate and an interdigitated flow field on a second side of said bipolar plate, a plate margin having a first header aperture formed therethrough, a first port formed therethrough between said first header aperture and said serpentine flow field, a second header aperture formed therethrough, and a second port formed therethrough between said second header aperture and said interdigitated flow field.
  • the method further comprises the step of assembling the bipolar plate into a PEM fuel cell comprises a first seal disposed on said second side of said bipolar plate and having a first passageway formed therein to define a first fluid transmission path between said first header and a second passageway formed therein to define a second fluid transmission path between said second port and said interdigitated flow field.
  • the method further comprises the step of assembling the bipolar plate into a PEM fuel cell comprises a second seal disposed on said first side of said bipolar plate and having a third passageway formed therein to define a third fluid communication path from said second header to said second port and a fourth passageway formed therein to define a fourth fluid communication path from said first port to said serpentine flow field.
  • the powdered host particle is a powder from any resin of a particle size greater than 5 ⁇ .
  • the conductive additive is comprised of graphite, graphene oxide, carbon nanotubes, carbon nanowires or any combination.
  • Another embodiment of the present invention includes a method of making a bipolar plate from a conductive composite structure made of coated particles for use in making a composite material for enhancing a property of the composite material, comprising: providing a powdered component called a powdered host particle; providing a second powdered component called a conductive additive that comprises a softening or melting temperature higher than the melting point of the powdered host particle; inputting said powdered host particle and the conductive additive into a ball mill; and ball milling said powdered host and the conductive additive for a milling time to sufficiently mix, but not melt, the powdered host particle into a conductive host- additive particle wherein the particle formed from the conductive additive and the powdered host particle is incorporated into a bipolar plate assembly for a fuel cell comprising: A bipolar plate comprising a formable resin with the conductive additive; a bipolar plate having a plurality of formed serpentine flow field on a first side of said bipolar plate and an interdigitated flow field on a second
  • the powder mixture is compressed and heated to form a composite structure resulting in the powdered host particle flowing in a direction orthogonal to the compression force and oriented the additive with the highest aspect ratio parallel to the flow of the powdered host particle wherein a preferential orientation of the electrical and thermal conductivity is obtained.
  • the preferential orientation of the electrical and thermal conductivity of the composite structure is parallel to the flow of the powdered host particle.
  • the method further comprises suspending the powder mixture in a carrier fluid and depositing the powder mixture on a surface after or during the deposition of a coating that is heated and/or compressed to form the composite structure.
  • the method further comprises adding an additive that comprises a highest aspect ratio and that is oriented to be parallel to surface of the substrate.
  • the powdered host particle is a powder from a polymer or metal.
  • the additive is comprised of graphite, graphene oxide, carbon nanotubes carbon nanowires or other carbon allotrope.
  • FIG. 1 shows a baseline composite with preferred orientation of the thermal and electrical conduction
  • FIG. 2 shows the baseline composite after separation into segments physically oriented to have orthogonal orientation of thermal and electrical conduction
  • FIG. 3 shows the assembled engineered composite with the different preferred orientation of the thermal and electrical conduction fused into the structure.
  • graphene refers to a polycyclic hexagonal lattice with carbon atoms covalently bonded to each other.
  • the covalently bonded carbon atoms can form a six-member ring as a repeating unit, and may also include at least one of a five-member ring and a seven- member ring.
  • Multiple graphene layers are referred to in the art as graphite.
  • graphene may be a single layer, or also may comprise multiple layers of graphene that are stacked on other layers of graphene yielding graphene oxide.
  • graphene oxide can have a maximum thickness of about 100 nanometers (nm), specifically about 0.5 nm to about 90 nm.
  • graphene oxide flake refers to a crystalline or “flake” form of graphene oxide that has been oxidized and includes many graphene sheets oxidized and stacked together and can have oxidation levels ranging from 0.01 % to 25% by weight in ultra pure water.
  • the flakes are preferably substantially flat.
  • PEM fuel cell refers to a proton exchange membrane fuel cell, but also referred to as a polymer electrolyte membrane (PEM) fuel cell that converts, e.g., hydrogen and ambient air into water and an electrical current.
  • PEM polymer electrolyte membrane
  • Graphite, graphene oxide, carbon nano tubes/fiber, and carbon black are collectively known as conductive components.
  • Undoped TPX® Polymethylpentene (PMP) characteristics include electrical insulating properties and strong hydrolysis resistance (TPX® is a registered trademark to Mitsui Chemical).
  • the PMP particles can be subjected to mechanochemical processing in what is generically referred to as a "ball mill.”
  • the PMP has a particle size greater than or equal to 2 ⁇ . When grinding in the ball mill, the balls (media) in their random movement are rolling against each other and the container, exerting shearing forces on the carbon black and the PMP particles.
  • the resulting PMP particles can be coated on the exterior and have not been melted nor has the particle's size been reduced by more than 20% due to the milling process.
  • the present invention includes the development of an engineered composite bipolar plate structure by using methods and materials that allow compression stamping/pressing processes combined with orienting different segments to optimize both electrical and mechanical performance and cost.
  • Graphite is commonly used to enhance strength, electrical, and thermal conductivity of a composite material.
  • Graphite has been used as a component in a wide number of composite materials including resins, epoxies, and polymers.
  • Composite plates can be prepared by using different reinforcing fillers such as natural graphite, synthetic graphite, carbon black, or carbon fibers with phenolic resin as a polymer matrix precursor in its liquid and powder form.
  • the composite plates prepared using the present invention were found to have the appropriate proportion of components for use in a wide variety of applications, e.g., plates, leads, connectors, or as components for fuel cells, e.g., bipolar plates.
  • the composite materials prepared in accordance with the present invention were characterized for physical and mechanical properties. It is found that by changing the component amounts for composite bipolar plates, improvements can be achieved that increase performance and decrease cost compared to that of pure graphite bipolar plates.
  • a 2-liter ball mill uses 3 lbs (or -2700 stainless steel balls) of 0.25" (6.35 mm) diameter stainless steel balls weighing up to about 1 gram each. Milling or mixing can be accomplished in a closed chamber for 5 to 100 minutes at 1 ,000 RPM or less to coat the host particles.
  • the other mills, such as sand, bead, and horizontal, use smaller media from 0.3 mm to 2 mm, but run at a very high rpm (roughly 100-1 ,000).
  • An attrition mill directly agitates the media to achieve grinding.
  • both impact action and shearing force are generally required.
  • the grinding media's random movement and spinning at different rotational energies exert shearing forces and impact forces on the carbon black and host particles.
  • the milling/mixing time may range from 5 to 60 minutes. The combination of milling/mixing speed, media size and milling/mixing time enables the production of a host particle covered with conductive additives.
  • the conductive composition of the composite can vary relative to each other but the inventors have found a ratio of: 77:3: 10 (graphite : graphene oxide (GO) : polymethylpentene (PMP)), weight-to-weight, exhibits the outstanding properties.
  • Other transparent polyolefin can be used with the present invention.
  • unique properties were achieved such as a bulk density less than 1.75 g/cm 3 , electrical conductivity greater than 250 S/cm, and Rockwell hardness > 80.
  • the skilled artisan will recognize that variations to the ratio can be made, without undue experimentation, to that yield: a bulk density less than 1.75 g/cm 3 , electrical conductivity greater than 250 S/cm, and Rockwell hardness > 80.
  • the structure is compressed to a minimum of 3,000 psi and heated up to 280° the polymethylpentene (PMP) TPX®, Mitsui Chemicals Inc., to melts and flows.
  • PMP polymethylpentene
  • TPX® polymethylpentene
  • capillary action associated pressure and flowing polymer draws the carbon additives to be parallel to the flow and perpendicular to the compressive force.
  • the orientation and densification of the compressed composite structure creates high electrical conductivity in the plane of the orientation and low electrical conductivity normal to the orientation.
  • the in-plane electrical conductivity can be several hundred S/cm to several thousand S/cm while the through-plane is substantially less than 100 S/cm.
  • the highly oriented structure has high mechanical strength in addition to the oriented conductivity.
  • the low through-plane conductivity limits the efficiency and performance of a BPP.
  • Combining and fusing different sections that have orthogonal orientations of high in-plane electrical conductivity forms a physical structure that has optimized conductivity both in-plane and through-plane.
  • Combining and fusing the segments are accomplished by placing a small amount of solvent containing a high loading of graphene oxide on the adjacent sides of the segments and then compressing them with a modest amount of heat resulting in a fully dense BPP structure with optimized conductivity both in-plane and through-plane. Where the net electrical conductivity of the final composite is given by the engineering combination of series and parallel resistors resulting from the assembled composite.
  • FIG. 1 shows a baseline composite with preferred orientation of the thermal and electrical conduction.
  • FIG. 2 shows the baseline composite after separation into segments physically oriented to have orthogonal orientation of thermal and electrical conduction.
  • FIG. 3 shows the assembled engineered composite with the different preferred orientation of the thermal and electrical conduction fused into the structure.
  • the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), "including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
  • A, B, C, or combinations thereof refers to all permutations and combinations of the listed items preceding the term.
  • A, B, C, or combinations thereof is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB.
  • expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, AB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth.
  • the present invention may also include methods and compositions in which the transition phrase "consisting essentially of or "consisting of may also be used.
  • words of approximation such as, without limitation, "about”, “substantial” or “substantially” refers to a condition that when so modified is understood to not necessarily be absolute or perfect but would be considered close enough to those of ordinary skill in the art to warrant designating the condition as being present.
  • the extent to which the description may vary will depend on how great a change can be instituted and still have one of ordinary skilled in the art recognize the modified feature as still having the required characteristics and capabilities of the unmodified feature.
  • a numerical value herein that is modified by a word of approximation such as "about” may vary from the stated value by at least ⁇ 1, 2, 3, 4, 5, 6, 7, 10, 12 or 15%.
  • compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.

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Abstract

This invention describes an engineered low-cost, lightweight, high-performance thermally and electrically conductive composite. Where the thermally and electrically conductive composite will be stamped, pressed, sprayed, or doctor bladed into the final form. The final structure can be in the form of a bipolar plate or other highly thermally and electrically conductive structures that includes flow channels or other mechanical or fluidic structure.

Description

ENGINEERED LOW-COST, HIGH-PERFORMANCE CONDUCTIVE COMPOSITE
TECHNICAL FIELD OF THE INVENTION
The present invention relates in general to the field of low-cost, high-performance composites.
BACKGROUND OF THE INVENTION
Without limiting the scope of the invention, its background is described in connection with compound conductive materials.
Bipolar plates are an important key component of fuel cells, flow batteries and electronic applications. Bipolar plates used in fuel cells are primarily used because of their ability to simultaneously provide a thermally and electrically conductive plate that also distributes and separates gases. Significant effort is aimed at reducing the weight and cost of bipolar plates for fuel cell applications. Weight and cost constraints make solving fundamental problems with bipolar plate performance. Poor chemical stability of metallic plates allows for resistive oxides to form on the plate surface, significantly reducing output electricity. Today, most bipolar plates are composed entirely of graphite or mostly graphite and a polymer filler to create a lightweight composite bipolar plate. Thus far, graphite has been an ideal candidate for composing bipolar plates because of its mechanical, chemical, thermal, gas barrier, electrical, flame retardant and other properties, however it suffers from poor electrical conductivity and high cost of manufacture.
SUMMARY OF THE INVENTION
The method herein enables the dispersion/compounding of graphite, carbon black, graphene oxide or any additive with a polymeric component that can be extruded, stamped, or otherwise mass-produced into a bipolar plate. The particles of the one material are coated with the material of another conductive component or multiple conductive components using a milling process. The coated surface of the material creates conductive connective pathways through the volume of the final composite structure. By controlling the ratio of the components, one can achieve low density, high electrical conductivity, and surface hardness required for mass process by extrusion stamping or other mass manufacturing process.
In one embodiment, the present invention includes a method of making a conductive, composite bipolar plate made of coated particles for making a composite material that enhances a property of the composite material, comprising: providing a powdered component called a powdered host particle; providing a second powdered component called a conductive additive that comprises a softening or melting temperature higher than the melting point of the powdered host particle; inputting said powdered host particle and said conductive additive into a ball mill; and ball milling said powdered host and said conductive additive for a milling time to sufficiently mix but not melt the powdered host particle into a conductive host-additive particle. In one aspect, the powdered host particle is a powder from a resin of polymethylpentene. In one aspect, the conductive additive is comprised of graphite, graphene oxide, carbon nanotubes, or carbon nanowires. In one aspect, the conductive host-additive particle is formed into a bipolar plate assembly for a PEM fuel cell, and the bipolar plate comprises a formable resin with one or more conductive materials. In one aspect, the conductive host-additive particle is formed into a bipolar plate assembly for a PEM fuel cell that comprises the bipolar plate having a plurality of formed serpentine flow field on a first side of said bipolar plate and an interdigitated flow field on a second side of said bipolar plate, a plate margin having a first header aperture formed therethrough, a first port formed therethrough between said first header aperture and said serpentine flow field, a second header aperture formed therethrough, and a second port formed therethrough between said second header aperture and said interdigitated flow field. In one aspect, the conductive host-additive particle is formed into a bipolar plate assembly for a PEM fuel cell that comprises a first seal disposed on said second side of said bipolar plate and having a first passageway formed therein to define a first fluid transmission path between said first header and a second passageway formed therein to define a second fluid transmission path between said second port and said interdigitated flow field. In one aspect, the conductive host- additive particle is formed into a bipolar plate assembly for a PEM fuel cell comprises a second seal disposed on said first side of said bipolar plate and having a third passageway formed therein to define a third fluid communication path from said second header to said second port and a fourth passageway formed therein to define a fourth fluid communication path from said first port to said serpentine flow field. In one aspect, the powdered host particle is a powder from any resin of a particle size greater than 5μιη. In one aspect, the powdered host particle is a powder from a resin of polymethylpentene. In one aspect, the conductive additive is comprised of graphite, graphene oxide, carbon nanotubes or carbon nanowires or any combination formed in situ in the ball mill prior to the addition of the powdered host particle.
Another embodiment of the present invention includes a method of making a conductive composite particle or material, comprising: providing a powdered host particle; providing a conductive additive with a softening or melting temperature higher than the melting point of the powdered host particle; mixing the powdered host particle and the powdered additive in a ball mill; and milling the powdered host and the powdered additive for a time sufficient to mix but not melt the powdered host particle to form an electrically conductive host-additive blend. In one aspect, the powdered host particle is a powder from a resin of polymethylpentene. In another aspect, the electrically conductive host-additive blend has at least one of the following properties: a bulk density less than 1.75 g/cm3, an electrical conductivity greater than 250 S/cm, or a Rockwell hardness > 80. In another aspect, the method further comprises the step of extruding, stamping, or otherwise mass-producing the electrically conductive host-additive blend into a bipolar plate. In another aspect, the bipolar plate is adapted for use in a PEM fuel cell, wherein the bipolar plate further comprises a formable resin with one or more conductive additives. In another aspect, the method further comprises the step of assembling the bipolar plate into a PEM fuel cell that comprises the bipolar plate having a plurality of formed serpentine flow field on a first side of said bipolar plate and an interdigitated flow field on a second side of said bipolar plate, a plate margin having a first header aperture formed therethrough, a first port formed therethrough between said first header aperture and said serpentine flow field, a second header aperture formed therethrough, and a second port formed therethrough between said second header aperture and said interdigitated flow field. In another aspect, the method further comprises the step of assembling the bipolar plate into a PEM fuel cell comprises a first seal disposed on said second side of said bipolar plate and having a first passageway formed therein to define a first fluid transmission path between said first header and a second passageway formed therein to define a second fluid transmission path between said second port and said interdigitated flow field. In another aspect, the method further comprises the step of assembling the bipolar plate into a PEM fuel cell comprises a second seal disposed on said first side of said bipolar plate and having a third passageway formed therein to define a third fluid communication path from said second header to said second port and a fourth passageway formed therein to define a fourth fluid communication path from said first port to said serpentine flow field. In another aspect, the powdered host particle is a powder from any resin of a particle size greater than 5μιη. In another aspect, the conductive additive is comprised of graphite, graphene oxide, carbon nanotubes, carbon nanowires or any combination.
Another embodiment of the present invention includes a method of making a bipolar plate from a conductive composite structure made of coated particles for use in making a composite material for enhancing a property of the composite material, comprising: providing a powdered component called a powdered host particle; providing a second powdered component called a conductive additive that comprises a softening or melting temperature higher than the melting point of the powdered host particle; inputting said powdered host particle and the conductive additive into a ball mill; and ball milling said powdered host and the conductive additive for a milling time to sufficiently mix, but not melt, the powdered host particle into a conductive host- additive particle wherein the particle formed from the conductive additive and the powdered host particle is incorporated into a bipolar plate assembly for a fuel cell comprising: A bipolar plate comprising a formable resin with the conductive additive; a bipolar plate having a plurality of formed serpentine flow field on a first side of said bipolar plate and an interdigitated flow field on a second side of said bipolar plate, a plate margin having a first header aperture formed therethrough, a first port formed therethrough between said first header aperture and said serpentine flow field, a second header aperture formed therethrough, and a second port formed therethrough between said second header aperture and said interdigitated flow field; a first seal disposed on said second side of said bipolar plate and having a first passageway formed therein to define a first fluid transmission path between said first header and a second passageway formed therein to define a second fluid transmission path between said second port and said interdigitated flow field; and a second seal disposed on said first side of said bipolar plate and having a third passageway formed therein to define a third fluid communication path from said second header to said second port and a fourth passageway formed therein to define a fourth fluid communication path from said first port to said serpentine flow field. In one aspect, the powder mixture is compressed and heated to form a composite structure resulting in the powdered host particle flowing in a direction orthogonal to the compression force and oriented the additive with the highest aspect ratio parallel to the flow of the powdered host particle wherein a preferential orientation of the electrical and thermal conductivity is obtained. In another aspect, the preferential orientation of the electrical and thermal conductivity of the composite structure is parallel to the flow of the powdered host particle. In another aspect, the method further comprises suspending the powder mixture in a carrier fluid and depositing the powder mixture on a surface after or during the deposition of a coating that is heated and/or compressed to form the composite structure. In another aspect, the method further comprises adding an additive that comprises a highest aspect ratio and that is oriented to be parallel to surface of the substrate. In another aspect, the powdered host particle is a powder from a polymer or metal. In another aspect, the additive is comprised of graphite, graphene oxide, carbon nanotubes carbon nanowires or other carbon allotrope.
BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of the features and advantages of the present invention, reference is now made to the detailed description of the invention along with the accompanying figures and in which: FIG. 1 shows a baseline composite with preferred orientation of the thermal and electrical conduction;
FIG. 2 shows the baseline composite after separation into segments physically oriented to have orthogonal orientation of thermal and electrical conduction; and
FIG. 3 shows the assembled engineered composite with the different preferred orientation of the thermal and electrical conduction fused into the structure.
DETAILED DESCRIPTION OF THE INVENTION
While the making and using of various embodiments of the present invention are discussed in detail below, it should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are illustrative of ways to make and use the invention and do not delimit the scope of the invention.
As used herein, the term "graphene" refers to a polycyclic hexagonal lattice with carbon atoms covalently bonded to each other. The covalently bonded carbon atoms can form a six-member ring as a repeating unit, and may also include at least one of a five-member ring and a seven- member ring. Multiple graphene layers are referred to in the art as graphite. Thus, graphene may be a single layer, or also may comprise multiple layers of graphene that are stacked on other layers of graphene yielding graphene oxide. Generally, graphene oxide can have a maximum thickness of about 100 nanometers (nm), specifically about 0.5 nm to about 90 nm.
As used herein, the term "graphene oxide flake" refers to a crystalline or "flake" form of graphene oxide that has been oxidized and includes many graphene sheets oxidized and stacked together and can have oxidation levels ranging from 0.01 % to 25% by weight in ultra pure water. The flakes are preferably substantially flat.
As used herein, the term "PEM fuel cell" refers to a proton exchange membrane fuel cell, but also referred to as a polymer electrolyte membrane (PEM) fuel cell that converts, e.g., hydrogen and ambient air into water and an electrical current. The present invention finds particular uses in PEM fuel cells.
Graphite, graphene oxide, carbon nano tubes/fiber, and carbon black are collectively known as conductive components. Undoped TPX® Polymethylpentene (PMP) characteristics include electrical insulating properties and strong hydrolysis resistance (TPX® is a registered trademark to Mitsui Chemical). The PMP particles can be subjected to mechanochemical processing in what is generically referred to as a "ball mill." The PMP has a particle size greater than or equal to 2μηι. When grinding in the ball mill, the balls (media) in their random movement are rolling against each other and the container, exerting shearing forces on the carbon black and the PMP particles. The resulting PMP particles can be coated on the exterior and have not been melted nor has the particle's size been reduced by more than 20% due to the milling process.
The present invention includes the development of an engineered composite bipolar plate structure by using methods and materials that allow compression stamping/pressing processes combined with orienting different segments to optimize both electrical and mechanical performance and cost.
Graphite is commonly used to enhance strength, electrical, and thermal conductivity of a composite material. Graphite has been used as a component in a wide number of composite materials including resins, epoxies, and polymers. Composite plates can be prepared by using different reinforcing fillers such as natural graphite, synthetic graphite, carbon black, or carbon fibers with phenolic resin as a polymer matrix precursor in its liquid and powder form. The composite plates prepared using the present invention were found to have the appropriate proportion of components for use in a wide variety of applications, e.g., plates, leads, connectors, or as components for fuel cells, e.g., bipolar plates. The composite materials prepared in accordance with the present invention were characterized for physical and mechanical properties. It is found that by changing the component amounts for composite bipolar plates, improvements can be achieved that increase performance and decrease cost compared to that of pure graphite bipolar plates.
A useful and simple equation describing the grinding momentum IS JB X V (mass x velocity), which enables a calculation of how the attrition mill fits into the family of ball mills. For example, a 2-liter ball mill uses 3 lbs (or -2700 stainless steel balls) of 0.25" (6.35 mm) diameter stainless steel balls weighing up to about 1 gram each. Milling or mixing can be accomplished in a closed chamber for 5 to 100 minutes at 1 ,000 RPM or less to coat the host particles. The other mills, such as sand, bead, and horizontal, use smaller media from 0.3 mm to 2 mm, but run at a very high rpm (roughly 100-1 ,000). High-speed dispersers with no media run at an even faster rpm (1,000-4,000). An attrition mill directly agitates the media to achieve grinding. For efficient fine grinding, both impact action and shearing force are generally required. The grinding media's random movement and spinning at different rotational energies exert shearing forces and impact forces on the carbon black and host particles. The milling/mixing time may range from 5 to 60 minutes. The combination of milling/mixing speed, media size and milling/mixing time enables the production of a host particle covered with conductive additives. The conductive composition of the composite can vary relative to each other but the inventors have found a ratio of: 77:3: 10 (graphite : graphene oxide (GO) : polymethylpentene (PMP)), weight-to-weight, exhibits the outstanding properties. Other transparent polyolefin can be used with the present invention. By controlling the ratio of components, unique properties were achieved such as a bulk density less than 1.75 g/cm3, electrical conductivity greater than 250 S/cm, and Rockwell hardness > 80. The skilled artisan will recognize that variations to the ratio can be made, without undue experimentation, to that yield: a bulk density less than 1.75 g/cm3, electrical conductivity greater than 250 S/cm, and Rockwell hardness > 80.
As the structure is compressed to a minimum of 3,000 psi and heated up to 280° the polymethylpentene (PMP) TPX®, Mitsui Chemicals Inc., to melts and flows. As the polymer melts and flows under compression, capillary action associated pressure and flowing polymer draws the carbon additives to be parallel to the flow and perpendicular to the compressive force. The orientation and densification of the compressed composite structure creates high electrical conductivity in the plane of the orientation and low electrical conductivity normal to the orientation. In a traditional bipolar plate (BPP), the in-plane electrical conductivity can be several hundred S/cm to several thousand S/cm while the through-plane is substantially less than 100 S/cm. The highly oriented structure has high mechanical strength in addition to the oriented conductivity. The low through-plane conductivity limits the efficiency and performance of a BPP. Combining and fusing different sections that have orthogonal orientations of high in-plane electrical conductivity forms a physical structure that has optimized conductivity both in-plane and through-plane. Combining and fusing the segments are accomplished by placing a small amount of solvent containing a high loading of graphene oxide on the adjacent sides of the segments and then compressing them with a modest amount of heat resulting in a fully dense BPP structure with optimized conductivity both in-plane and through-plane. Where the net electrical conductivity of the final composite is given by the engineering combination of series and parallel resistors resulting from the assembled composite.
FIG. 1 shows a baseline composite with preferred orientation of the thermal and electrical conduction. FIG. 2 shows the baseline composite after separation into segments physically oriented to have orthogonal orientation of thermal and electrical conduction. FIG. 3 shows the assembled engineered composite with the different preferred orientation of the thermal and electrical conduction fused into the structure.
Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed, that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.
It will be understood that particular embodiments described herein are shown by way of illustration and not as limitations of the invention. The principal features of this invention can be employed in various embodiments without departing from the scope of the invention. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific procedures described herein. Such equivalents are considered to be within the scope of this invention and are covered by the claims.
All publications and patent applications mentioned in the specification are indicative of the level of skill of those skilled in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.
The use of the word "a" or "an" when used in conjunction with the term "comprising" in the claims and/or the specification may mean "one," but it is also consistent with the meaning of "one or more," "at least one," and "one or more than one." The use of the term "or" in the claims is used to mean "and/or" unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and "and/or." Throughout this application, the term "about" is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects.
As used in this specification and claim(s), the words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include") or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
The term "or combinations thereof as used herein refers to all permutations and combinations of the listed items preceding the term. For example, "A, B, C, or combinations thereof is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, AB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context. In certain embodiments, the present invention may also include methods and compositions in which the transition phrase "consisting essentially of or "consisting of may also be used.
As used herein, words of approximation such as, without limitation, "about", "substantial" or "substantially" refers to a condition that when so modified is understood to not necessarily be absolute or perfect but would be considered close enough to those of ordinary skill in the art to warrant designating the condition as being present. The extent to which the description may vary will depend on how great a change can be instituted and still have one of ordinary skilled in the art recognize the modified feature as still having the required characteristics and capabilities of the unmodified feature. In general, but subject to the preceding discussion, a numerical value herein that is modified by a word of approximation such as "about" may vary from the stated value by at least ±1, 2, 3, 4, 5, 6, 7, 10, 12 or 15%.
All of the compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.

Claims

What is claimed is:
1. A method of making a conductive composite structure made of coated particles for use in making a composite material for enhancing a property of the composite material, comprising: providing a powdered component called a powdered host particle;
providing a second powdered component called a conductive additive that comprises a softening or melting temperature higher than the melting point of the powdered host particle; inputting said powdered host particle and the conductive additive into a ball mill; and ball milling said powdered host and the conductive additive for a milling time to sufficiently mix, but not melt, the powdered host particle into a conductive host-additive particle.
2. The method of claim 1 , wherein the powder mixture is compressed and heated to form a composite structure resulting in the powdered host particle flowing in a direction orthogonal to the compression force and oriented the additive with the highest aspect ratio parallel to the flow of the powdered host particle wherein a preferential orientation of the electrical and thermal conductivity is obtained.
3. The method of claim 3, wherein the preferential orientation of the electrical and thermal conductivity of the composite structure is parallel to the flow of the powdered host particle.
4. The method of claim 1, further comprising suspending the powder mixture in a carrier fluid and depositing the powder mixture on a surface after or during the deposition of a coating that is heated and/or compressed to form the composite structure.
5. The method of claim 1 , further comprising adding an additive that comprises a highest aspect ratio and that is oriented to be parallel to surface of the substrate.
6. The method of claim 1, wherein the powdered host particle is a powder from a polymer or metal.
7. The method of claim 1, wherein the additive is comprised of graphite, graphene oxide, carbon nanotubes carbon nanowires or other carbon allotrope.
8. The method of claim 2, further comprising cutting the composite material into elements and combined with the preferential orientation at alternating structures with an alternating pattern of high conductivity relative to the main composite.
9. The method of claim 8, wherein the composite alternating structures are held in place by coating the insert with a layer of solvent and carbon additive that fuse to the main composite structure when heated and compressed.
10. The method of claim 2, wherein conductive host-additive particle is incorporated into a bipolar plate assembly for a fuel cell comprising: a. A bipolar plate comprising a formable resin with the conductive additive;
b. a bipolar plate having a plurality of formed serpentine flow field on a first side of said bipolar plate and an interdigitated flow field on a second side of said bipolar plate, a plate margin having a first header aperture formed therethrough, a first port formed therethrough between said first header aperture and said serpentine flow field, a second header aperture formed therethrough, and a second port formed therethrough between said second header aperture and said interdigitated flow field;
c. a first seal disposed on said second side of said bipolar plate and having a first passageway formed therein to define a first fluid transmission path between said first header and a second passageway formed therein to define a second fluid transmission path between said second port and said interdigitated flow field; and d. a second seal disposed on said first side of said bipolar plate and having a third passageway formed therein to define a third fluid communication path from said second header to said second port and a fourth passageway formed therein to define a fourth fluid communication path from said first port to said serpentine flow field.
11. The method of Claim 1 , wherein the powdered host particle is a powder from any resin of a particle size greater than 5μιη.
12. The method of Claim 1 , wherein the powdered host particle is a powder from a resin of polymethylpentene.
13. The method of Claim 1 , wherein the conductive additive is comprised of graphite, graphene oxide, carbon nanotubes, carbon nanowires or other carbon allotrope in any combination.
14. A method of making a bipolar plate from a conductive composite structure made of coated particles for use in making a composite material for enhancing a property of the composite material, comprising:
providing a powdered component called a powdered host particle;
providing a second powdered component called a conductive additive that comprises a softening or melting temperature higher than the melting point of the powdered host particle; inputting said powdered host particle and the conductive additive into a ball mill; and ball milling said powdered host and the conductive additive for a milling time to sufficiently mix, but not melt, the powdered host particle into a conductive host-additive particle wherein the particle formed from the conductive additive and the powdered host particle is incorporated into a bipolar plate assembly for a fuel cell comprising:
a bipolar plate comprising a formable resin with the conductive additive;
a bipolar plate having a plurality of formed serpentine flow field on a first side of said bipolar plate and an interdigitated flow field on a second side of said bipolar plate, a plate margin having a first header aperture formed therethrough, a first port formed therethrough between said first header aperture and said serpentine flow field, a second header aperture formed therethrough, and a second port formed therethrough between said second header aperture and said interdigitated flow field;
a first seal disposed on said second side of said bipolar plate and having a first passageway formed therein to define a first fluid transmission path between said first header and a second passageway formed therein to define a second fluid transmission path between said second port and said interdigitated flow field; and
a second seal disposed on said first side of said bipolar plate and having a third passageway formed therein to define a third fluid communication path from said second header to said second port and a fourth passageway formed therein to define a fourth fluid communication path from said first port to said serpentine flow field.
15. The method of claim 14, wherein the powder mixture is compressed and heated to form a composite structure resulting in the powdered host particle flowing in a direction orthogonal to the compression force and oriented the additive with the highest aspect ratio parallel to the flow of the powdered host particle wherein a preferential orientation of the electrical and thermal conductivity is obtained.
16. The method of claim 14, wherein the preferential orientation of the electrical and thermal conductivity of the composite structure is parallel to the flow of the powdered host particle.
17. The method of claim 14, further comprising suspending the powder mixture in a carrier fluid and depositing the powder mixture on a surface after or during the deposition of a coating that is heated and/or compressed to form the composite structure.
18. The method of claim 14, further comprising adding an additive that comprises a highest aspect ratio and that is oriented to be parallel to surface of the substrate.
19. The method of claim 14, wherein the powdered host particle is a powder from a polymer or metal.
20. The method of claim 14, wherein the additive is comprised of graphite, graphene oxide, carbon nanotubes carbon nanowires or other carbon allotrope.
PCT/US2017/027231 2016-04-12 2017-04-12 Engineered low-cost, high-performance conductive composite WO2017180759A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6348279B1 (en) * 1998-04-10 2002-02-19 Nisshinbo Industries, Inc. Separator for polymeric electrolyte fuel cell having a roughened surface
US20020119358A1 (en) * 2001-02-23 2002-08-29 Rock Jeffrey A. Stamped bipolar plate for PEM fuel cell stack
US7329698B2 (en) * 2001-08-06 2008-02-12 Showa Denko K.K. Conductive curable resin composition and separator for fuel cell
US20080318110A1 (en) * 2007-06-19 2008-12-25 Gm Global Technology Operations, Inc. Thermoplastic bipolar plate
WO2017053204A1 (en) * 2015-09-21 2017-03-30 Garmor Inc. Low-cost, high-performance composite bipolar plate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6348279B1 (en) * 1998-04-10 2002-02-19 Nisshinbo Industries, Inc. Separator for polymeric electrolyte fuel cell having a roughened surface
US20020119358A1 (en) * 2001-02-23 2002-08-29 Rock Jeffrey A. Stamped bipolar plate for PEM fuel cell stack
US7329698B2 (en) * 2001-08-06 2008-02-12 Showa Denko K.K. Conductive curable resin composition and separator for fuel cell
US20080318110A1 (en) * 2007-06-19 2008-12-25 Gm Global Technology Operations, Inc. Thermoplastic bipolar plate
WO2017053204A1 (en) * 2015-09-21 2017-03-30 Garmor Inc. Low-cost, high-performance composite bipolar plate

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