WO2018111968A1 - Ensembles plaques-électrodes bipolaires et empilements de cellules électrochimiques et batteries à flux liquide produites à partir de ceux-ci - Google Patents

Ensembles plaques-électrodes bipolaires et empilements de cellules électrochimiques et batteries à flux liquide produites à partir de ceux-ci Download PDF

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Publication number
WO2018111968A1
WO2018111968A1 PCT/US2017/065964 US2017065964W WO2018111968A1 WO 2018111968 A1 WO2018111968 A1 WO 2018111968A1 US 2017065964 W US2017065964 W US 2017065964W WO 2018111968 A1 WO2018111968 A1 WO 2018111968A1
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WIPO (PCT)
Prior art keywords
electrically conductive
electrode assembly
flow
plate
major surface
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PCT/US2017/065964
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English (en)
Inventor
Raymond P. Johnston
Gregory M. Haugen
Brian T. Weber
Onur S. Yordem
Bharat R. Acharya
Brandon A. Bartling
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3M Innovative Properties Company
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Publication of WO2018111968A1 publication Critical patent/WO2018111968A1/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
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • 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
    • H01M8/0206—Metals or alloys
    • 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
    • H01M8/0221—Organic resins; Organic polymers
    • 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
    • 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
    • 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
    • H01M8/023—Porous and characterised by the material
    • H01M8/0234—Carbonaceous material
    • 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
    • H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
    • H01M8/0256—Vias, i.e. connectors passing through the separator material
    • 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
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention generally relates to assemblies useful in the fabrication of electrochemical cells and batteries.
  • the present invention relates to bipolar plate-electrode assemblies (BPPEAs) and electrochemical cells, electrochemical cell stacks and liquid flow batteries produced therefrom.
  • BPPEAs bipolar plate-electrode assemblies
  • the disclosure further provides methods of making the monopolar plate-electrode assemblies.
  • the present disclosure provides a bipolar plate-electrode assembly comprising (A) a first monopolar plate-electrode assembly including (i) a first flow plate substrate having a first major surface and an opposed second major surface in the x-y plane of the first monopolar plate electrode assembly, wherein the first major surface includes at least one first flow channel, allowing fluid flow in the x-y plane of the first monopolar plate electrode assembly, wherein the depth of the at least one first flow channel extends through the thickness of the first flow plate substrate and wherein the at least one first flow channel is in fluid communication with a first fluid inlet port and a first fluid outlet port of the first flow plate substrate; (ii) a first porous electrode material contained in at least a portion of the at least one first flow channel; and (iii) a first electrically conductive layer in contact with the second major surface of the first flow plate substrate, wherein the first electrically conductive layer is impervious to fluid; and (B) a second monopolar plate-electrode assembly including (i)
  • the first monopolar plate-electrode assembly may exhibit electrical communication through the thickness of the first flow plate substrate and may not exhibit fluid communication through the thickness of the first flow plate substrate and/or the second monopolar plate-electrode assembly may exhibit electrical communication through the thickness of the second flow plate substrate and may not exhibit fluid communication through the thickness of the second flow plate substrate.
  • the depth of the at least one second flow channel extends through the thickness of the second flow plate substrate and the second flow plate substrate further comprises a second porous electrode material contained in at least a portion of the at least one second flow channel.
  • the second flow plate substrate includes at least one via intersecting the channel bottom of the at least one second flow channel and the second major surface of the second flow plate substrate and wherein the second flow plate substrate further includes ii) a second porous electrode material contained in at least a portion of the at least one second flow channel; and (iii) a second electrically conductive material contained in at least a portion of the at least one via of the second flow plate substrate, wherein the second electrically conductive material is in electrical communication with the second porous electrode material
  • the present disclosure provides a method of making a bipolar plate-electrode assembly including, providing a first monopolar plate-electrode assembly, which includes (i) a first flow plate substrate having a first major surface and an opposed second major surface in the x-y plane of the first monopolar plate electrode assembly, wherein the first major surface includes at least one first flow channel, allowing fluid flow in the x-y plane of the first monopolar plate electrode assembly, wherein the depth of the at least one first flow channel extends through the thickness of the first flow plate substrate and wherein the at least one first flow channel is in fluid communication with a first fluid inlet port and a first fluid outlet port of the first flow plate substrate, (ii) a first porous electrode material contained in at least a portion of the at least one first flow channel, and (iii) a first electrically conductive layer in contact with the second major surface of the first flow plate substrate, wherein the first electrically conductive layer is impervious to fluid and the electrically conductive layer is an electrically conductive
  • the present disclosure provides an electrochemical cell stack for a liquid flow battery including at least one bipolar plate-electrode assembly according to any one of the bipolar plate-electrode assemblies of the present disclosure.
  • the present disclosure provides an electrochemical cell stack for a liquid flow battery comprising two electrochemical cells, each including two half cells and corresponding electrodes, and a bipolar plate-electrode assembly according to any one of the bipolar plate- electrode assemblies of the present disclosure, wherein a half cell from each of the two electrochemical cells includes a monopolar plate-electrode assembly of the bipolar plate- electrode assembly.
  • the present disclosure provides liquid flow battery including at least one bipolar plate-electrode assembly according to any one of the bipolar plate- electrode assemblies of the present disclosure.
  • the present disclosure provides a liquid flow battery comprising two electrochemical cells, each including two half cells and corresponding electrodes, and a bipolar plate-electrode assembly according to any one of the bipolar plate-electrode assemblies of the present disclosure, wherein a half cell from each of the two electrochemical cells includes a monopolar plate- electrode assembly of the bipolar plate-electrode assembly.
  • FIG. 1 A is a schematic top view of an exemplary flow plate substrate according to one exemplary embodiment of the present disclosure.
  • FIG. IB is a schematic bottom view of the exemplary flow plate substrate of FIG. 1 A according to one exemplary embodiment of the present disclosure.
  • FIG. 1C is a schematic cross-sectional side view of the exemplary flow plate substrate of FIG. 1 A according to one exemplary embodiment of the present disclosure.
  • FIG. ID is a schematic side view of the front face or back face of the exemplary flow plate substrate of FIG. 1 A according to one exemplary embodiment of the present disclosure.
  • FIG. 2A is a schematic top view of an exemplary monopolar plate-electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 2B is a schematic bottom view of the exemplary monopolar plate-electrode assembly of FIG. 2A according to one exemplary embodiment of the present disclosure.
  • FIG. 2C is a schematic cross-sectional side view of the exemplary monopolar plate- electrode assembly of FIG. 2 A according to one exemplary embodiment of the present disclosure.
  • FIG. 2D is a schematic side view of the front face or back face of the exemplary monopolar plate-electrode assembly of FIG. 2 A according to one exemplary embodiment of the present disclosure.
  • FIG. 3 A is a schematic top view of an exemplary flow plate substrate according to one exemplary embodiment of the present disclosure.
  • FIG. 3B is a schematic bottom view of the exemplary flow plate substrate of FIG. 3 A according to one exemplary embodiment of the present disclosure.
  • FIG. 3C is a schematic cross-sectional side view of the exemplary flow plate substrate of FIG. 3 A according to one exemplary embodiment of the present disclosure.
  • FIG. 3D is a schematic side view of the front face or back face of the exemplary flow plate substrate of FIG. 3 A according to one exemplary embodiment of the present disclosure.
  • FIG. 4A is a schematic top view of an exemplary monopolar plate-electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 4B is a schematic bottom view of the exemplary monopolar plate-electrode assembly of FIG. 4A according to one exemplary embodiment of the present disclosure.
  • FIG. 4C is a schematic cross-sectional side view of the exemplary monopolar plate- electrode assembly of FIG. 4 A according to one exemplary embodiment of the present disclosure.
  • FIG. 4D is a schematic side view of the front face or back face of the exemplary monopolar plate-electrode assembly of FIG. 4 A according to one exemplary embodiment of the present disclosure.
  • FIG. 5A is a schematic top view of an exemplary flow plate substrate according to one exemplary embodiment of the present disclosure.
  • FIG. 5B is a schematic bottom view of the exemplary flow plate substrate of FIG. 5 A according to one exemplary embodiment of the present disclosure.
  • FIG. 5C is a schematic cross-sectional side view of the exemplary flow plate substrate of FIG. 5 A according to one exemplary embodiment of the present disclosure.
  • FIG. 5D is a schematic side view of the front face or back face of the exemplary flow plate substrate of FIG. 5 A according to one exemplary embodiment of the present disclosure.
  • FIG. 6A is a schematic top view of an exemplary monopolar plate-electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 6B is a schematic bottom view of the exemplary monopolar plate-electrode assembly of FIG. 6A according to one exemplary embodiment of the present disclosure.
  • FIG. 6C is a schematic cross-sectional side view of the exemplary monopolar plate- electrode assembly of FIG. 6 A according to one exemplary embodiment of the present disclosure.
  • FIG. 6D is a schematic side view of the front face or back face of the exemplary monopolar plate-electrode assembly of FIG. 6 A according to one exemplary embodiment of the present disclosure.
  • FIG. 6C-1 is a schematic cross-sectional side view of an exemplary monopolar plate- electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 6C-2 is a schematic cross-sectional side view of an exemplary monopolar plate- electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 6C-3 is a schematic cross-sectional side view of an exemplary monopolar plate- electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 7A is a schematic cross-sectional side view of the exemplary bipolar plate- electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 7B is a schematic cross-sectional side view of the exemplary bipolar plate- electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 7C is a schematic cross-sectional side view of the exemplary bipolar plate- electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 7D is a schematic cross-sectional side view of the exemplary bipolar plate- electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 7E is a schematic cross-sectional side view of the exemplary bipolar plate- electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 7F is a schematic cross-sectional side view of the exemplary bipolar plate- electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 7G is a schematic cross-sectional side view of the exemplary bipolar plate- electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 7H is a schematic cross-sectional side view of the exemplary bipolar plate- electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 8 is a schematic cross-sectional side view of an exemplary electrochemical cell stack according to one exemplary embodiment of the present disclosure.
  • FIG. 9 is a schematic cross-sectional side view of an exemplary single cell, liquid flow battery according to one exemplary embodiment of the present disclosure.
  • non-conductive refers to a material or substrate that is non-electrically conductive, unless otherwise stated. In some embodiments, a material or substrate is non-electrically conductive if it has an electrical resistivity of greater than 1000 ohm-m.
  • a material or substrate is electrically conductive if it has an electrical resistivity of less than 1000 ohm-m, less than 1 ohm-m, less than 0.001 ohm-m, less than 0.0001 ohm-m or even less than 0.00001 ohm-m.
  • an aqueous based solution is defined as a solution wherein the solvent includes at least 50% water by weight.
  • a non-aqueous based solution is defined as a solution wherein the solvent contains less than 50% water by weight.
  • fluid communication between a first surface and a second surface of a substrate means that a fluid, e.g. gas and/or liquid, is capable of flowing continuously from a first surface of the substrate, through the thickness of a substrate, to a second surface of the substrate.
  • a fluid e.g. gas and/or liquid
  • impervious to fluid means fluid cannot pass through a substrate via fluid flow caused by an external force, e.g. gravity or an applied load.
  • a substrate that allows diffusive mass transport but not fluid flow caused by an external force may be considered to be impervious to fluid.
  • Softening Temperature is the glass transition temperature and/or the melting temperature of a polymer.
  • an integral structure includes a structure that can be held in any orientation in space and does not separate into at least two components, due to the force of gravity.
  • a single electrochemical cell which may be used in the fabrication of a liquid flow battery (e.g. a redox flow battery), generally, includes two porous electrodes, an anode and a cathode; an ion permeable membrane disposed between the two electrodes, providing electrical insulation between the electrodes and providing a path for one or more select ionic species to pass between the anode and cathode half-cells; anode and cathode flow plates, the former positioned adjacent the anode and the later positioned adjacent the cathode, each containing one or more channels which allow the anolyte and catholyte electrolytic solutions to contact and penetrate into the anode and cathode, respectively.
  • a liquid flow battery e.g. a redox flow battery
  • the flow plates are considered to be monopolar flow plates.
  • the flow plate includes one or more channels on its first major surface and one or more channels on it second major surface, the flow plate is considered to be a bipolar flow plate.
  • one set of channels of the bipolar flow plate would include anolyte and the other set of channels would include catholyte.
  • the cell In a redox flow battery containing a single electrochemical cell (cell consists of an anode monopolar plate and cathode monopolar plate) or a cell stack of multiple electrochemical cells (cell stack includes monopolar flow plates, one cathode and one anode, each at one end of the cell stack and bipolar flow plates there between), for example, the cell would also include two current collectors, one adjacent to and in contact with the exterior surface of the anode monopolar flow plate and one adjacent to and in contact with the exterior surface of the cathode monopolar flow plate. The current collectors allow electrons generated during cell discharge to connect to an external circuit and do useful work.
  • a functioning redox flow battery or electrochemical cell stack also includes an anolyte, anolyte reservoir and corresponding fluid distribution system (piping and at least one or more pumps) to facilitate flow of anolyte into the anode half-cells, and a catholyte, catholyte reservoir and corresponding fluid distribution system to facilitate flow of catholyte into the cathode half-cells.
  • anolyte anolyte reservoir and corresponding fluid distribution system
  • piping and at least one or more pumps to facilitate flow of anolyte into the anode half-cells
  • a catholyte, catholyte reservoir and corresponding fluid distribution system to facilitate flow of catholyte into the cathode half-cells.
  • redox flow cells and batteries have the unique feature of being able to store their energy outside the main body of the electrochemical cell, i.e. in the anolyte.
  • the amount of storage capacity is mainly limited by the amount of anolyte and catholyte, the concentration of active species and the state of charge of the active species, in these solutions.
  • redox flow batteries may be used for large scale energy storage needs associated with wind farms and solar energy plants, for example, by scaling the size of the reservoir tanks and active species concentrations, accordingly.
  • Redox flow cells also have the advantage of having their storage capacity being independent of their power.
  • the power in a redox flow battery or cell is generally determined by the size and number of electrochemical cells (sometimes referred to in total as a "stack") within the battery. Additionally, as redox flow batteries are being designed for electrical grid use, the voltages must be high. However, the voltage of a single redox flow electrochemical cell is generally less than 3 volts
  • Electrodes e.g. anode and cathode
  • the ion permeable membrane disposed there between and the anode and cathode flow plates, e.g. an anode flow plate and a cathode flow plate.
  • Cell stacks would further include bipolar flow plates disposed between adjacent ion permeable membranes.
  • the materials selected for these components are critical to performance, as well as, the cost of the cell.
  • each of these components is provided individually within a cell or battery as an individual component and this fact can lead to significant assembly cost for each cell.
  • Materials used for the electrodes may be based on carbon, e.g. graphite, which provides desirable catalytic activity for the oxidation/reduction reactions to occur and is electrically conductive to provide electron transfer to the flow plates.
  • the electrode materials may be porous, to provide greater surface area for the oxidation/reduction reactions to occur.
  • Porous electrodes may include porous electrically conductive materials.
  • Porous electrodes may include carbon fiber based papers, felts, and cloths.
  • Porous electrodes may also include porous dielectric materials that include at least one electrically conductive coating to enable electrically conductivity.
  • Porous electrodes may also include polymer-electrically conductive particulate composites.
  • the electrolyte may penetrate into the body of the electrode, access the additional surface area for reaction and thus increase the rate of energy generation per unit volume of the electrode.
  • the anolyte and catholyte may be water based, i.e. an aqueous solution
  • Surface treatments may be used to enhance the hydrophilicity of the redox flow electrodes. This is in contrast to fuel cell electrodes which typically are designed to be hydrophobic, to prevent moisture from entering the electrode and corresponding catalyst layer/region, and to facilitate removal of moisture from the electrode region in, for example, a hydrogen/oxygen based fuel cell.
  • the monopolar anode flow plate and the monopolar cathode flow plate which are used to fabricate the bipolar plate-electrode assemblies of the present disclosure, are electrically conductive and may be fabricated from metals or other electrically conductive materials, such as, an electrically conductive polymer or electrically conductive polymer composite. Significant cost may be incurred due to the cost of the materials and the costs associated with the fabrication of the plate, e.g. the formation of the at least one flow channel.
  • the monopolar anode and cathode flow plates may be fabricated by a variety of techniques including machining (e.g. milling), molding (e.g. injection molding), embossing and combinations thereof.
  • the present disclosure provides bipolar plate-electrode assemblies fabricated from unique monopolar plate-electrode assemblies.
  • the monopolar plate-electrode assemblies combine a flow plate substrate (cathode or anode flow plate substrate) with a porous electrode material contained in at least a portion of the at least one flow channel of the flow plate substrate. In so doing, two layers of an electrochemical cell or battery may be combined into a single layer, which may reduce cell and/or battery assembly costs.
  • the depth of the at least one flow channel extends through the thickness of the first flow plate substrate of the monopolar plate-electrode assemblies of the present disclosure and a porous electrode material is contained in at least a portion of the at least one flow channel.
  • the porous electrical material intersects both the first major surface and second major surface of the first flow plate substrate, thereby allowing electrical communication through the thickness of the first flow plate substrate.
  • An electrically conductive layer may be in contact with the second major surface of the flow plate substrate and the porous electrode material. The electrically conductive layer is in electrical communication with the porous electrode material.
  • the monopolar plate-electrode assemblies of the present disclosure provide electrical communication between the first major surface and the second major surface of the flow plate substrate, through the porous electrode material and then through the electrically conductive layer.
  • the bottom of the at least one flow channel of the monopolar plate-electrode assemblies of the present disclosure may intersect at least one via, that extends through the remaining thickness of the flow plate substrate, and an electrically conductive material is contained in at least a portion of the at least one via.
  • the electrically conductive material is in electrical
  • the monopolar plates of the present disclosure provide electrical communication between the first major surface and the second major surface of the flow plate substrate, through the porous electrode material and the electrically conductive material within the at least one via.
  • the bipolar plate-electrode assembly may exhibit electrical communication through the thickness of the flow plate substrates and may not exhibit fluid communication through the thickness of the flow plate substrates.
  • two monopolar plate electrode assemblies are configured adjacent one another such that each of their major surfaces, which include the at least one flow channel, are exterior surfaces of the bipolar plate-electrode assembly and their respective opposed major surfaces are adjacent to one another, with the two flow plates in electrical communication with each other.
  • This may be achieved by having the two opposed major surfaces in direct contact with each other, such that they are in electrical
  • the bipolar plate-electrode assemblies of the present disclosure there is electrical communication through the thickness of the bipolar plate-electrode assembly.
  • the flow plate substrate need not be fabricated from an expensive conductive material and may, in turn, be fabricated from an inexpensive and/or easily processed dielectric material, e.g. a dielectric polymer. However, this is not a limitation and the flow plate substrate may be fabricated from electrically conductive materials.
  • the flow plate substrate, porous electrode material, electrically conductive material (if used) and electrically conductive layer (if used) of a monopolar-plate electrode assembly may form an integral structure and will be referred to as a monopolar plate-electrode assembly.
  • the monopolar plate-electrode assembly may be used in an electrochemical cell and/or liquid flow battery.
  • the flow plate substrates, porous electrode materials, electrically conductive materials (if used) and electrically conductive layers (if used) of a bipolar-plate electrode assembly may form an integral structure, i.e. the two monopolar plate-electrode assemblies comprising a bipolar plate electrode assembly may form an integral structure, and will be referred to as a bipolar plate-electrode assembly.
  • the at least one electrically conductive layer may be impervious to fluid.
  • the bipolar plate-electrode assembly may further include a first ion permeable membrane adjacent to a major surface of the first monopolar plate; the flow plate substrate surface that includes the at least one flow channel.
  • the bipolar plate-electrode assembly may further include a second ion permeable membrane adjacent to the major surface of the second monopolar plate; the flow plate substrate surface that includes the at least one flow channel.
  • the bipolar plate-electrode assembly may further include a first discontinuous transport protection layer adjacent the major surface of the first monopolar plate, the flow plate substrate surface that includes the at least one flow channel.
  • the bipolar plate-electrode assembly may further include a second discontinuous transport protection layer adjacent to the major surface of the second monopolar plate, the flow plate substrates surface that includes the at least one flow channel.
  • at least one, optional, ion permeable membrane at least one, optional, discontinuous transport protection layer may be disposed between the ion permeable membrane and the flow plate substrate.
  • the discontinuous transport protection layer protects the ion permeable membrane from puncture by materials that comprise the porous electrode material, e.g. carbon fibers, and thus prevents localized shorting.
  • transport within the phrase “transport protection layer” refers to fluid transport within and/or through the protection layer.
  • the bipolar plate-electrode assemblies are useful in the fabrication of liquid flow, e.g. redox flow, electrochemical cell stacks and batteries. Liquid flow
  • electrochemical cell stacks and batteries may include cells and batteries having a single half- cell of a cell being a liquid flow type or both half-cells of a cell being a liquid flow type.
  • the present disclosure further provides methods of fabricating bipolar plate assemblies useful in liquid flow electrochemical cells, electrochemical cell stacks, and batteries.
  • the present disclosure provides bipolar plate-electrode assemblies comprising (A) a first monopolar plate-electrode assembly including (i) a first flow plate substrate having a first major surface and an opposed second major surface in the x-y plane of the first monopolar plate electrode assembly, wherein the first major surface includes at least one first flow channel, allowing fluid flow in the x-y plane of the first monopolar plate electrode assembly, wherein the depth of the at least one first flow channel extends through the thickness of the first flow plate substrate and wherein the at least one first flow channel is in fluid communication with a first fluid inlet port and a first fluid outlet port of the first flow plate substrate; (ii) a first porous electrode material contained in at least a portion of the at least one first flow channel; and (iii) a first electrically conductive layer in contact with the second major surface of the first flow plate substrate; and (B) a second monopolar plate- electrode assembly including a second flow plate substrate having a first major surface and an opposed second major surface in the x-y
  • the first monopolar plate- electrode assembly may exhibit electrical communication through the thickness of the first flow plate substrate and may not exhibit fluid communication through the thickness of the first flow plate substrate and/or the second monopolar plate-electrode assembly may exhibit electrical communication through the thickness of the second flow plate substrate and may not exhibit fluid communication through the thickness of the second flow plate substrate.
  • the second monopolar plate-electrode assembly includes a second flow plate substrate that includes at least one via intersecting the channel bottom of the at least one second flow channel and the second major surface of the second flow plate substrate and wherein the second flow plate substrate further includes ii) a second porous electrode material contained in at least a portion of the at least one second flow channel; and (iii) a second electrically conductive material contained in at least a portion of the at least one via of the second flow plate substrate, wherein the second electrically conductive material is in electrical communication with the second porous electrode material.
  • the second monopolar plate-electrode assembly includes a second flow plate substrate wherein the depth of the at least one second flow channel extends through the thickness of the second flow plate substrate and the second flow plate substrate further comprises a second porous electrode material contained in at least a portion of the at least one second flow channel.
  • the second monopolar plate-electrode assembly may further include a second electrically conductive layer in contact with the second major surface of the second flow plate substrate, and the second flow plate substrate does not exhibit fluid communication between the first major surface and the second major surface, through the thickness of the second flow plate substrate.
  • the second electrically conductive layer may be impervious to fluid
  • the flow plate substrate e.g. first and/or second flow plate substrate
  • the flow plate substrate is an electrically conductive flow plate substrate.
  • the flow plate substrate e.g. first and/or second flow plate substrate
  • the flow plate substrate is a dielectric flow plate substrate.
  • the second flow plate substrate includes at least one via
  • the at least one via of the second flow plate substrate may each be a single via or a plurality of vias.
  • the electrically conductive material e.g. the first and/or second electrically conductive material, may be impervious to fluid.
  • the bipolar plate- electrode assemblies of the present disclosure may include at least one electrically conductive layer adjacent to and/or in contact with both the second major surface of the first flow plate substrate and the second major surface of the second flow plate substrate.
  • the electrically conductive layer may be impervious to fluid.
  • the porous electrode material e.g. first and/or second porous electrode material
  • the electrically conductive material and/or the at least one electrically conductive layer may include electrically conductive particulate, e.g.
  • the porous electrode material e.g. first and/or second porous electrode material
  • the electrically conductive material e.g. first and/or second electrically conductive material
  • the at least one electrically conductive layer may include at least one of a metal film, an electrically conductive particulate and an electrically conductive polymer composite; the electrically conductive polymer composite may include polymer and the electrically conductive particulate.
  • the electrically conductive particulate may include at least one of metal particulate, electrically conductive carbon particulate and electrically conductive polymer particulate.
  • at least one of the distal surface of the first major surface of the first flow plate substrate and the first major surface of the second flow plate substrate may be free of porous electrode material and/or a conventional electrode, e.g. carbon fiber mat.
  • the distal surface of the second major surface of the flow plate substrate may be free of electrically conductive material.
  • at least a portion (up to and including all) of the distal surface of the first major surface of the flow plate substrate may include a layer of porous electrode material.
  • At least a portion (up to and including all) of the distal surface of the second major surface of the flow plate substrate may include a layer of porous electrode material or electrically conductive material. In some embodiments, at least a portion (up to and including all) of the distal surface of both the first major surface and second major surface of the flow plate substrate may include a layer of porous electrode material. If at least a portion of the distal surface of any of the major surfaces of the first and/or second flow plate substrates includes a layer of porous electrode material and/or a layer of electrically conductive material, the layer of porous electrode material and the layer of electrically conductive material may be considered to be part of the major surface of the flow plate substrate. In some embodiments, the thickness of the flow plate substrate, e.g. first and/or second flow plate substrate, may be from 0.025 cm to 3.2 cm.
  • the bipolar plate-electrode assembly may include an, optional, first ion permeable membrane disposed adjacent the first major surface of the first flow plate substrate.
  • the bipolar plate-electrode assembly may include at least one of a first ion permeable membrane disposed adjacent the first major surface of the first flow plate substrate and a second ion permeable membrane disposed adjacent the first major surface of the second flow plate substrate.
  • the bipolar plate-electrode assembly may include an, optional, first discontinuous transport protection layer disposed adjacent the first major surface of the first flow plate substrate.
  • the bipolar plate-electrode assembly may include at least one of a first discontinuous transport protection layer disposed adjacent the first major surface of the first flow plate substrate and a second discontinuous transport protection layer disposed adjacent the first major surface of the second flow plate substrate.
  • Embodiments that contain an ion permeable membrane may further include a discontinuous transport protection layer disposed between the ion permeable membrane and the first major surface of the flow plate substrate.
  • FIGS. 1 A through ID, FIGS. 3 A through 3D and FIGS 5A through 5D show various, non-limiting, embodiments of flow plate substrates suitable for monopolar plate-electrode assemblies and bipolar plate-electrode assemblies of the present disclosure
  • FIGS. 2A through 2D, FIGS. 4 A through 4D and FIGS. 6 A through 6D show the corresponding exemplary monopolar plate-electrode assemblies utilizing the flow plate substrates of FIGS. 1 A through ID, FIGS. 3A through 3D and FIGS 6A-6D, respectively.
  • the monopolar plate- electrode assemblies are suitable for use in bipolar plate-electrode assemblies of the present disclosure.
  • FIG. 1 A is a schematic top view and FIG.
  • IB is a schematic bottom view of exemplary flow plate substrate 10 according to one embodiment of the present disclosure.
  • Flow plate substrate 10 has a first major surface 10a and an opposed second major surface 10b (see FIG. IB), at least one flow channel 20 with a bottom 20b (see FIG. 1C) in fluid communication with a fluid inlet port 30a (represented by the imaginary, dashed lines) and a fluid outlet port 30b (represented by the imaginary, dashed lines) and includes at least one via 40 intersecting the channel bottom 20b of the at least one flow channel 20.
  • the at least one via 40 is a plurality of vias 40.
  • the flow plate substrate has a front face lOff and a back face lObf.
  • IB shows a schematic bottom view of the exemplary flow plate substrate 10 of FIG. 1A and includes second major surface 10b and the at least one via 40.
  • FIG. 1C shows a schematic cross-sectional side view of the exemplary flow plate substrate 10 of FIG. 1 A through line 1C.
  • Flow plate substrate 10 of FIG. 1C includes first major surface 10a and second major surface 10b, at least one flow channel 20 having channel bottom 20b and a depth, D, a width, W, and at least one via 40, having a height, H, intersecting the channel bottom 20b of the at least one flow channel 20 and the second major surface 10b.
  • ID is a schematic side view of the front face or back face (in this exemplary embodiment, the flow plate substrate is symmetrical and the front face and back face views are identical) of the exemplary flow plate substrate 10 of FIG. 1A.
  • Flow plate substrate 10 of FIG. ID shows front face lOff or back face lObf and includes first major surface 10a and second major surface 10b and inlet port 30a of front face lOff or outlet port 30b of back face lObf.
  • Flow plate substrate 10 has thickness, T.
  • FIGS. 2A through 2D are schematic views of an exemplary monopolar plate-electrode assembly 100 which includes the flow plate substrate 10 of FIGS. 1 A through ID, according to one exemplary embodiment of the present disclosure.
  • FIG. 2A is a schematic top view
  • FIG. 2B is a schematic bottom view
  • FIG. 2C is a schematic cross-sectional side view, though line 2C of FIG. 2A
  • FIG. 2D is a schematic side view of the front face or back face of the exemplary monopolar plate-electrode assembly 100.
  • Monopolar plate-electrode assembly 100 includes flow plate substrate 10, as previously described.
  • Flow plate substrate 10 has first major surface 10a and opposed second major surface 10b in the x-y plane of the monopolar plate.
  • First major surface 10a includes at least one flow channel 20, allowing fluid flow in the x-y plane of the monopolar plate. Additionally, monopolar plate-electrode assembly 100 includes porous electrode material 50 contained in at least a portion of the at least one flow channel 20 and an electrically conductive material 60 contained in at least a portion of the at least one via 40, wherein the electrically conductive material 60 is in electrical communication with porous electrode material 50. monopolar plate-electrode assembly 100 exhibits electrical communication between first major surface 10a and second major surface 10b, through the thickness of the flow plate substrate (z-axis), but does not exhibit fluid communication between first major surface 10a and second major surface 10b, through the thickness of the flow plate substrate (z-axis). FIG.
  • FIG. 2D shows a schematic side view of the front face lOOff or back face lOObf of the monopolar plate-electrode assembly 100 of FIG. 2A.
  • the monopolar plate-electrode assembly is symmetrical and the front face and back face views are identical.
  • Monopolar plate-electrode assembly 100 may further include, optional, electrically conductive layer 70 adjacent to and in contact with the second major surface of the flow plate substrate.
  • the electrically conductive layer is impervious to fluid.
  • FIG. 3 A is a schematic top view and FIG. 3B is a schematic bottom view of exemplary flow plate substrate 11 according to one embodiment of the present disclosure.
  • Flow plate substrate 11 has a first major surface 11a and an opposed second major surface 1 lb (see FIG. 3B), at least one flow channel 20 with a bottom 20b (see FIG. 3C) in fluid communication with a fluid inlet port 30a (represented by the imaginary, dashed lines) and a fluid outlet port 30b (represented by the imaginary, dashed lines) and includes at least one via 40 intersecting the channel bottom 20b of the at least one flow channel 20.
  • the at least one via 40 is a single via.
  • the single via may span the entire width and length (x-y dimensions) of flow channel 20.
  • FIG. 3B shows a schematic bottom view of the exemplary flow plate substrate 11 of FIG. 3 A and includes second major surface 1 lb and the at least one via 40.
  • FIG. 3C shows a schematic cross-sectional side view of the exemplary flow plate substrate 11 of FIG. 3A through line 3C.
  • Flow plate substrate 11 of FIG. 3C includes first major surface 11a and second major surface 1 lb, at least one flow channel 20 having channel bottom 20b and a depth, D, a width, W, and at least one via 40, having a height, H, intersecting the channel bottom 20b of the at least one flow channel 20 and the second major surface 1 lb.
  • FIG. 3D is a schematic side view of the front face or back face (in this exemplary embodiment, the flow plate substrate is symmetrical and the front face and back face views are identical) of the exemplary flow plate substrate 11 of FIG. 3A.
  • Flow plate substrate 11 of FIG. 3D shows front face 1 Iff or back face 1 lbf and includes first major surface 11a and second major surface 1 lb and inlet port 30a of front face 1 Iff or outlet port 30b of back face 1 lbf.
  • Flow plate substrate 11 has thickness, T.
  • FIGS. 4A through 4D are schematic views of an exemplary monopolar plate-electrode assembly 101 which includes the flow plate substrate 11 of FIGS. 3A through 3D, according to one exemplary embodiment of the present disclosure.
  • FIG. 4A is a schematic top view
  • FIG. 4B is a schematic bottom view
  • FIG. 4C is a schematic cross-sectional side view, though line 4C of FIG. 4A
  • FIG. 4D is a schematic side view of the front face or back face of the exemplary monopolar plate-electrode assembly 101.
  • Monopolar plate-electrode assembly 101 includes flow plate substrate 11, as previously described.
  • Flow plate substrate 11 has first major surface 11a and opposed second major surface 1 lb in the x-y plane of the monopolar plate.
  • First major surface 11a includes at least one flow channel 20, allowing fluid flow in the x-y plane of the monopolar plate.
  • monopolar plate-electrode assembly 101 includes porous electrode material 50 contained in at least a portion of the at least one flow channel 20 and an electrically conductive material 60 contained in at least a portion of the at least one via 40, wherein the electrically conductive material 60 is in electrical communication with porous electrode material 50.
  • Monopolar plate-electrode assembly 101 exhibits electrical communication between first major surface 11a and second major surface 1 lb, through the thickness of the flow plate substrate, but does not exhibit fluid communication between first major surface 11a and second major surface 1 lb through the thickness of the flow plate substrate.
  • FIG. 4D shows a schematic side view of the front face lOlff or back face lOlbf of the monopolar plate-electrode assembly 101 of FIG. 1 A.
  • the monopolar plate-electrode assembly is symmetrical and the front face and back face views are identical.
  • Monopolar plate-electrode assembly 101 may further include, optional, electrically conductive layer 70 adjacent to and in contact with the second major surface of the flow plate substrate.
  • the electrically conductive layer is impervious to fluid.
  • FIG. 5A is a schematic top view and FIG. 5B is a schematic bottom view of exemplary flow plate substrate 12 according to one embodiment of the present disclosure.
  • Flow plate substrate 12 has a first major surface 12a and an opposed second major surface 12b (see FIG. 5B), at least one flow channel 20 in fluid communication with a fluid inlet port 30a (represented by the imaginary, dashed lines) and a fluid outlet port 30b (represented by the imaginary, dashed lines).
  • the flow plate substrate has a front face 12ff and a back face 12bf.
  • FIG. 5B shows a schematic bottom view of the exemplary flow plate substrate 12 of FIG. 5A and includes second major surface 12b.
  • FIG. 5C shows a schematic cross-sectional side view of the exemplary flow plate substrate 12 of FIG.
  • FIG. 5D is a schematic side view of the front face or back face (in this exemplary embodiment, the flow plate substrate is symmetrical and the front face and back face views are identical) of the exemplary flow plate substrate 12 of FIG. 5A.
  • Flow plate substrate 12 of FIG. 5D shows front face 12ff or back face 12bf and includes first major surface 12a and second major surface 12b and inlet port 30a of front face 12ff or outlet port 30b of back face 12bf.
  • Flow plate substrate 12 has thickness, T.
  • FIGS. 6A through 6D are schematic views of an exemplary monopolar plate-electrode assembly 102 which includes the flow plate substrate 12 of FIGS. 5A through 5D, according to one exemplary embodiment of the present disclosure.
  • FIG. 6A is a schematic top view
  • FIG. 6B is a schematic bottom view
  • FIG. 6C is a schematic cross-sectional side view, though line 6C of FIG. 6A
  • FIG. 6D is a schematic side view of the front face or back face of the exemplary monopolar plate-electrode assembly 102.
  • Monopolar plate-electrode assembly 102 includes flow plate substrate 12, as previously described.
  • Flow plate substrate 12 has first major surface 12a and opposed second major surface 12b in the x-y plane of the monopolar plate.
  • First major surface 12a includes at least one flow channel 20, allowing fluid flow in the x-y plane of the monopolar plate.
  • monopolar plate-electrode assembly 102 includes porous electrode material 50 contained in at least a portion of the at least one flow channel 20 and electrically conductive layer 70 adjacent to and in contact with the second major surface 12b of the flow plate substrate 12, wherein the electrically conductive layer 70 is in electrical communication with porous electrode material 50.
  • Monopolar plate-electrode assembly 102 exhibits electrical communication between first major surface 12a and second major surface 12b, through the thickness of the flow plate substrate (z-axis), but does not exhibit fluid communication between first major surface 12a and second major surface 12b through the thickness of the flow plate substrate (z-axis), as electrically conductive layer 70 is impervious to fluid flow and prevents fluid communication between first major surface 12a and second major surface 12b through the at least one flow channel 20 and the porous electrode material 50 contained therein.
  • FIG. 6D shows a schematic side view of the front face 102ff or back face 102bf of the monopolar plate- electrode assembly 102 of FIG. 6A.
  • the monopolar plate- electrode assembly is symmetrical and the front face and back face views are identical.
  • the porous electrode material enables electrical communication between the first major surface and the second major surface of the flow plate substrate, through the thickness of the flow plate substrate. This may be particularly beneficial when the flow plate substrate is a dielectric flow plate substrate.
  • embodiments include an electrically conductive layer in contact with the second major surface of the flow plate substrate, wherein the first electrically conductive layer is impervious to fluid.
  • the fluid impervious electrically conductive layer inhibits fluid communication between the first major surface and the second major surface of the flow plate substrate, through the thickness of the flow plate substrate.
  • the porous electrode material combined with the electrically conductive material (contained within the at least one via) in electrical communication therewith enable the monopolar-plate electrode assemblies to have electrical communication through the thickness of the flow plate substrate (between the first major surface and the second major surface of the flow plate substrate). This may be particularly beneficial when the flow plate substrate is a dielectric flow plate substrate.
  • the electrically conductive material is impervious to fluid. As such, in some embodiments, the fluid impervious electrically conductive material inhibits fluid
  • an optional electrically conductive layer which is impervious to fluid, may be used to inhibit fluid communication between the first major surface and the second major surface of the flow plate substrate, i.e. the monopolar plate electrode assembly and does not exhibit fluid communication through the thickness of the flow plate substrate.
  • FIG. 6C-1 is a schematic cross-sectional side view of an exemplary monopolar plate- electrode assembly 102-1, similar to monopolar plate-electrode assembly 102 of FIG. 6C, except monopolar plate-electrode assembly 102-1 further includes an ion permeable membrane 80 adjacent to first major surface 12a of flow plate substrate 12.
  • ion permeable membrane 80 is adjacent to and in contact with first major surface 12a of flow plate substrate 12.
  • Any of the monopolar plate- electrode assemblies of the present disclosure e.g. monopolar plate-electrode assemblies 100, 101 and 102, may include an ion permeable membrane adjacent to the first major surface of the flow plate substrate.
  • FIG. 6C-2 is a schematic cross-sectional side view of an exemplary monopolar plate- electrode assembly 102-2, similar to monopolar plate-electrode assembly 102 of FIG. 6C, except monopolar plate-electrode assembly 102-2 further includes a discontinuous transport protection layer 90 adjacent to first major surface 12a of flow plate substrate 12.
  • discontinuous transport protection layer 90 is adjacent to and in contact with first major surface 12a of flow plate substrate 12.
  • Any of the monopolar plate-electrode assemblies of the present disclosure e.g. monopolar plate- electrode assemblies 100, 101 and 102, may include a discontinuous transport protection layer adjacent to the first major surface of the flow plate substrate.
  • FIG. 6C-3 is a schematic cross-sectional side view of an exemplary monopolar plate- electrode assembly 102-3, similar to monopolar plate-electrode assembly 102 of FIG. 6C, except monopolar plate-electrode assembly 102-3 further includes an ion permeable membrane 80 adjacent to first major surface 12a of flow plate substrate 12 and a
  • discontinuous transport protection layer 90 disposed between ion permeable membrane 80 and first major surface 12a of flow plate substrate 12.
  • discontinuous transport protection layer 90 is adjacent to and in contact with first major surface 12a of flow plate substrate 12 and ion permeable membrane 80 is adjacent to and in contact with discontinuous transport protection layer 90.
  • Any of the monopolar plate- electrode assemblies of the present disclosure e.g. monopolar plate-electrode assemblies 100, 101 and 102, may include an ion permeable membrane adjacent to the first major surface of the flow plate substrate and a discontinuous transport protection layer disposed between the ion permeable membrane and the first major surface of the flow plate substrate.
  • an ion permeable membrane may be adhered to the first major surface of the flow plate substrate of the monopolar plate-electrode assembly, the ion permeable membrane thereby being integral to and part of the monopolar plate-electrode assembly.
  • the electrically conductive layer may be adhered to the second major surface of the monopolar plate-electrode assembly, the electrically conductive layer thereby being integral to and part of the monopolar plate-electrode assembly.
  • a discontinuous transport protection layer may be adhered to the first major surface of the flow plate substrate, the discontinuous transport protection layer thereby being integral to and part of the monopolar plate-electrode assembly.
  • Embodiments which include a discontinuous transport protection layer adhered to the first major surface of the flow plate substrate may further include an ion permeable membrane adhered to the exposed surface of the discontinuous transport protection layer, the ion permeable membrane thereby being integral to and part of the monopolar plate-electrode assembly.
  • Substrates may be directly adhered to one another without the aid of an additional adhesive or substrates may be adhered to one another through the use of conventional adhesives.
  • FIGS. 7 A through 7H show schematic cross-sectional side views of various, non-limiting, exemplary bipolar plate-electrode assemblies according to the present disclosure.
  • FIG. 7A shows a schematic cross-sectional side view of bipolar plate electrode assembly 500-1.
  • Bipolar plate-electrode assembly 500-1 includes a first monopolar plate- electrode assembly 102 (left half of FIG. 7 A), as previously described (see FIGS. 6 A through 6D and corresponding text).
  • First monopolar plate-electrode assembly 102 includes first flow plate substrate 12, as previously described (see FIG.
  • the first major surface includes at least one first flow channel 20, allowing fluid flow in the x-y plane of the monopolar plate-electrode assembly, the at least one first flow channel is in fluid communication with a first fluid inlet port and a first fluid outlet port of the flow plate substrate (fluid inlet and outlet ports are indicated by the dotted lines in FIG. 7 A.
  • First monopolar plate-electrode assembly 102 includes a first porous electrode material 50 contained in at least a portion of at least one first flow channel 20 and electrically conductive layer 70 adjacent to and in contact with the second major surface of the flow plate substrate 12, wherein the electrically conductive layer 70 is in electrical communication with porous electrode material 50.
  • First flow plate substrate 12 may exhibit electrical communication between its first major surface and second major surface, through the thickness of first flow plate substrate 12, but may not exhibit fluid communication between its first major surface and second major surface, through the thickness of flow plate substrate 12.
  • the first monopolar plate-electrode assembly may exhibit electrical communication through the thickness of its flow plate substrate (between its first major surface and second major surface), but may does not exhibit fluid communication through the thickness of its flow plate substrate (between its first major surface and second major surface).
  • Bipolar plate-electrode assembly 500-1 includes a second monopolar plate-electrode assembly 102 (right half of FIG. 7 A), as previously described.
  • the second monopolar plate- electrode assembly includes a second flow plate substrate 12 having a first major surface and an opposed second major surface in the x-y plane of the bipolar plate-electrode assembly, wherein the first major surface includes at least one second flow channel 20, allowing fluid flow in the x-y plane of the second monopolar plate-electrode assembly.
  • the at least one second flow channel 20 is in fluid communication with a second fluid inlet port and a second fluid outlet port of second flow plate substrate, and the second major surface of second flow plate substrate is adjacent to the second major surface of the first flow plate substrate.
  • Second monopolar plate-electrode assembly 102 includes a second porous electrode material 50 contained in at least a portion of at least one first flow channel 20.
  • second monopolar plate-electrode assembly 102 does not include the electrically conductive layer 70, as shown previously in FIG. 6C, although this is not a limitation.
  • Second monopolar plate-electrode assembly 102 may include a second electrically conductive layer 70 adjacent to first electrically conductive layer 70 and adjacent to and in contact with the second major surface second flow plate substrate 12.
  • second porous electrode material 50 is in electrical communication with first electrically conductive layer 70 and there is electrical communication through the thickness of the bipolar plate-electrode assembly, e.g.
  • the second monopolar plate-electrode assembly may exhibit electrical communication through the thickness of its flow plate substrate (between its first major surface and second major surface), but may does not exhibit fluid communication through the thickness of its flow plate substrate (between its first major surface and second major surface)
  • the second monopolar plate-electrode assembly is nearly identical to first monopolar plate-electrode assembly 102, (except for the lack of second electrically conductive layer 70).
  • this is not a requirement, and other monopolar plate electrode assemblies of the present disclosure may be used for the second monopolar plate-electrode assembly (see FIG.
  • a conventional monopolar plate-electrode assembly which includes a conventional monopolar plate and a convention porous electrode material, e.g. carbon fiber mat (see FIG. 7D, for example), may be used for the second monopolar plate-electrode assembly.
  • a conventional monopolar plate-electrode assembly which includes a conventional monopolar plate and a convention porous electrode material, e.g. carbon fiber mat (see FIG. 7D, for example), may be used for the second monopolar plate-electrode assembly.
  • FIG. 7B shows a schematic cross-sectional side view of bipolar plate electrode assembly 500-2.
  • Bipolar plate-electrode assembly 500-2 is nearly identical to bipolar plate electrode assembly 500-1, as previously described, except the second monopolar plate- electrode assembly 102 has been replaced by second monopolar plate-electrode assembly 100, as previously described (see FIGS. 2A-2D and the corresponding text).
  • monopolar plate-electrode assembly 100 does not include optional electrically conductive layer 70, as shown in the previous figures.
  • Electrically conductive layer 70 shown in FIG. 7B, is the electrically conductive layer of first monopolar plate-electrode assembly 102.
  • the electrically conductive material 60 of at least one via 40 of second monopolar plate-electrode assembly 100 is in electrical communication with electrically conductive layer 70 and there is electrical communication through the thickness of the bipolar plate-electrode assembly, e.g. electrical communication through the thickness of the flow plate substrates.
  • the at least one via 40 of monopolar plate electrode assembly 100 is a plurality of vias.
  • FIG. 7C shows a schematic cross-sectional side view of bipolar plate electrode assembly 500-3.
  • Bipolar plate-electrode assembly 500-3 is nearly identical to bipolar plate electrode assembly 500-1, as previously described, except the second monopolar plate- electrode assembly 102 has been replaced by second monopolar plate-electrode assembly 101, as previously described (see FIGS. 2A-2D and the corresponding text).
  • monopolar plate-electrode assembly 101 does not include optional electrically conductive layer 70, as shown in the previous figures.
  • Electrically conductive layer 70 shown in FIG. 7C is the electrically conductive layer of first monopolar plate-electrode assembly 102.
  • the electrically conductive material 60 of at least one via 40 of second monopolar plate-electrode assembly 101 is in electrical communication with electrically conductive layer 70 and there is electrical communication through the thickness of the bipolar plate-electrode assembly, e.g. electrical communication through the thickness of the flow plate substrates.
  • the at least one via 40 of monopolar plate electrode assembly 101 is a single via.
  • FIG. 7D shows a schematic cross-sectional side view of bipolar plate electrode assembly 500-4.
  • Bipolar plate-electrode assembly 500-4 is nearly identical to bipolar plate electrode assembly 500-1, as previously described, except second monopolar plate-electrode assembly 102 has been replaced by second monopolar plate-electrode assembly 105.
  • Second monopolar plate-electrode assembly 105 includes a second flow plate substrate 15, a conventional electrically conductive flow plate substrate, having a first major surface and an opposed second major surface in the x-y plane of the bipolar plate-electrode assembly.
  • the first major surface of second flow plate substrate 15 includes at least one second flow channel 20, allowing fluid flow in the x-y plane of the second monopolar plate-electrode assembly 105.
  • the at least one second flow channel is in fluid communication with a second fluid inlet port and a second fluid outlet port of second flow plate substrate 15 (fluid inlet and outlet ports are indicated by the dotted lines in FIG. 7D), and the second major surface of second flow plate substrate 15 is adjacent to the second major surface of first flow plate substrate 12.
  • Second monopolar plate-electrode assembly further includes conventional electrode 55, a convention porous electrode, e.g. carbon fiber mat. Additionally, there is electrical communication through the thickness of the bipolar plate-electrode assembly, e.g. electrical communication through the thickness of the flow plate substrates.
  • bipolar plate electrode assemblies of the present disclosure electrical communication through the thickness of the flow plate substrates may be facilitated by having the first monopolar plate electrode assembly in electrical communication with the second monopolar plate electrode assembly via direct contact between the two substrates or via an intervening electrically conductive layer.
  • the bipolar plate electrode assemblies of the present disclosure include an electrically conductive layer adjacent to and in contact with both the second major surface of the first flow plate substrate and the second major surface of the second flow plate substrate.
  • the electrically conductive layers may include multiple layers.
  • the electrically conductive layer is impervious to fluid.
  • the electrically conductive layer adheres the second major surface of the first flow plate substrate to the second major surface of the second flow plate substrate, forming a bipolar plate-electrode assembly.
  • the electrically conductive layer is at least one of an electrically conductive pressure sensitive adhesive, an electrically conductive hot melt adhesive and an electrically conductive thermosetting adhesive.
  • the bipolar plate electrode assemblies of the present disclosure may further include at least one of a first ion permeable membrane disposed adjacent the first major surface of the first flow plate substrate and a second ion permeable membrane disposed adjacent the first major surface of the second flow plate substrate.
  • bipolar plate electrode assemblies of the present disclosure may include a first ion permeable membrane disposed adjacent the first major surface of the first flow plate substrate.
  • bipolar plate electrode assemblies of the present disclosure may include a second ion permeable membrane disposed adjacent the first major surface of the second flow plate substrate.
  • bipolar plate electrode assemblies of the present disclosure may include at least one of a first ion permeable membrane disposed adjacent to and in contact with the first major surface of the first flow plate substrate and a second ion permeable membrane disposed adjacent to and in contact with the first major surface of the second flow plate substrate.
  • FIG. 7E shows a schematic cross-sectional side view of bipolar plate electrode assembly 500-5.
  • Bipolar plate-electrode assembly 500-5 is nearly identical to bipolar plate electrode assembly 500-1, as previously described, except bipolar plate electrode assembly 500-5 further includes a first ion permeable membrane 80 disposed adjacent the first major surface of first flow plate substrate 12.
  • ion permeable membrane 80 is adjacent to and in contact with the first major surface of the first flow plate substrate 12.
  • FIG. 7F shows a schematic cross-sectional side view of bipolar plate electrode assembly 500-6.
  • Bipolar plate-electrode assembly 500-6 is nearly identical to bipolar plate electrode assembly 500-2, as previously described, except bipolar plate electrode assembly 500-6 further includes a first ion permeable membrane 80 disposed adjacent the first major surface of first flow plate substrate 12 and a second ion permeable membrane disposed adjacent the first major surface of the second flow plate substrate 100.
  • first ion permeable membrane 80 is disposed adjacent to and in contact with the first major surface of first flow plate substrate 12 and second ion permeable membrane 80 is disposed adjacent to the first major surface of second flow plate substrate 10. .
  • the bipolar plate electrode assemblies of the present disclosure may further include at least one of a first discontinuous transport protection layer disposed adjacent the first major surface of the first flow plate substrate and a second discontinuous transport protection layer disposed adjacent the first major surface of the second flow plate substrate.
  • bipolar plate electrode assemblies of the present disclosure may include a first discontinuous transport protection layer disposed adjacent the first major surface of the first flow plate substrate.
  • bipolar plate electrode assemblies of the present disclosure may include a second discontinuous transport protection layer disposed adjacent the first major surface of the second flow plate substrate.
  • bipolar plate electrode assemblies of the present disclosure may include at least one of a first discontinuous transport protection layer disposed adjacent to and in contact with the first major surface of the first flow plate substrate and a second discontinuous transport protection layer disposed adjacent to and in contact with the first major surface of the second flow plate substrate.
  • the bipolar plate electrode assemblies may further include a first discontinuous transport protection layer disposed between the first ion permeable membrane and the first major surface of the first flow plate substrate and/or a second discontinuous transport protection layer disposed between the second ion permeable membrane and the first major surface of the second flow plate substrate.
  • FIG. 7G shows a schematic cross-sectional side view of bipolar plate electrode assembly 500-7.
  • Bipolar plate-electrode assembly 500-7 is similar to bipolar plate electrode assembly 500-3, as previously described, except for the following modifications.
  • Bipolar plate electrode assembly 500-7 further includes a first ion permeable membrane 80 disposed adjacent the first major surface of the first flow plate substrate 12 and a second ion permeable membrane 80 disposed adjacent the first major surface of the second flow plate substrate 11.
  • the bipolar plate electrode assembly 500-7 includes a first ion permeable membrane 80 disposed adjacent to and in contact with the first major surface of the first flow plate substrate 12.
  • Bipolar plate-electrode assembly 500-7 also includes a discontinuous transport protection layer 90 disposed between second ion permeable membrane 80 and the first major surface of the second flow plate substrate 11.
  • Discontinuous transport protection layer 90 is adjacent to and in contact with the first major surface of second flow plate substrate 11 and is also adjacent to and in contact with second ion permeable membrane 80.
  • FIG. 7H shows a schematic cross-sectional side view of bipolar plate electrode assembly 500-8.
  • Bipolar plate-electrode assembly 500-8 is similar to bipolar plate electrode assembly 500-4, as previously described, except for the following modifications.
  • Bipolar plate electrode assembly 500-8 further includes a first ion permeable membrane 80 disposed adjacent the first major surface of the first flow plate substrate 12 and a second ion permeable membrane 80 disposed adjacent the first major surface of the second flow plate substrate 15.
  • the bipolar plate electrode assembly 500-8 includes a first discontinuous transport protection layer 90 disposed between first ion permeable membrane 80 and the first major surface of flow plate substrate 12 and a second discontinuous transport protection layer 90 disposed between second ion permeable membrane 80 and the first major surface of second flow plate substrate 15.
  • the first discontinuous transport protection layer 90 is adjacent to and in contact with the first major surface of first flow plate substrate 12 and is also adjacent to and in contact with first ion permeable membrane 80.
  • the second discontinuous transport protection layer 90 is adjacent to and in contact with conventional electrode 55 and is also adjacent to and in contact with second ion permeable membrane 80.
  • the flow plate substrate of the present disclosure may be an electrically conductive flow plate substrate or a dielectric flow plate substrate, i.e. a non-electrically conductive flow plate substrate. Fabrication of the flow plate substrate may include known techniques in the art and the fabrication techniques may be selected based on the material of the flow plate substrate. In some embodiments, the flow plate substrate along with the at least one flow channel and/or the at least one via, if present, of the flow plate substrate may be formed in a single fabrication step, e.g. molding or insert molding, to form a flow plate substrate, or may be formed in multiple steps, e.g.
  • calendaring, extruding and/or molding to form a solid flow plate substrate of the desired thickness followed by one or more machining steps to form the at least one flow channel and/or the at least one via.
  • Combinations of conventional machining techniques may be used to form the flow plate substrate.
  • Combinations of one or more conventional machining techniques and conventional molding, calendaring and/or extrusion techniques may also be used to form the flow plate substrate.
  • the at least one flow channel and the at least one via, if present, of the flow plate substrate may be formed in the flow plate substrate using conventional machining techniques including, but not limited to, milling, sawing, boring, drilling, turning, laser cutting, water jet cutting and the like.
  • the flow plate substrate may also be formed by additive manufacturing methods like direct writing, laser sintering, 3- dimensional printing and the like.
  • the electrically conductive material contained in at least a portion of the at least one via of the flow plate substrate is included in the flow plates substrate simultaneously while forming the at least one via.
  • a plurality of electrically conductive pins e.g. metal pins, may be placed in the mold prior to injection of the polymer into the mold.
  • the at least one via e.g.
  • a plurality of vias in this example, of the flow plate substrate is formed by the polymer flowing around the plurality of electrically conductive pins.
  • the plurality of vias are simultaneous filled by the electrically conductive material, i.e. the plurality of pins.
  • the pins may be removed from the flow plate substrate, leaving a plurality of vias.
  • the pins may have a diameter or greatest dimension with respect to their cross-section of between 0.1 mm and 10 mm, between 0.1 mm and 5 mm, between 0.1 mm and 1 mm, between 0.3 mm and 10 mm, between 0.3 mm and 5 mm, between 0.3 mm and 1 mm, between 0.5 mm and 10 mm, between 0.5 mm and 5 mm or even between 0.5 mm and 1 mm.
  • the dimensions, length, width and thickness, of the flow plate substrate are not particularly limited.
  • the thickness, T, (z-axis dimension, relative to FIGS. 1A-1D, for example) of the flow plate substrate may be from 0.025 cm to 3.2 cm, from 0.025 cm to 2.2 cm, from 0.025 cm to 1.2 cm, from 0.05 cm to 3.2 cm, from 0.05 cm to 2.2 cm, from 0.05 cm to 1.2 cm, from 0.1 cm to 3.2 cm, from 0.1 cm to 2.2 cm, or even from 0.1 cm to 1.2 cm.
  • the width (x-axis dimension, relative to FIGS. 1 A-ID, for example) of the flow plate substrate may be from 1 cm to 160 cm, from 1 cm to 120 cm, from 1 cm to 80 cm, from 10 cm to 160 cm, from 10 cm to 120 cm, from 10 cm to 80 cm, from 20 cm to 160 cm, from 20 cm to 120 cm, or even from 20 cm to 80 cm.
  • the width (x-axis dimension, relative to FIGS. 1 A-ID, for example) of the flow plate substrate may be from 1 cm to 160 cm, from 1 cm to 120 cm, from 1 cm to 80 cm, from 10 cm to 160 cm, from 10 cm to 120 cm, from 10 cm to 80 cm, from 20 cm to 160 cm, from 20 cm to 120 cm, or even from 20 cm to 80 cm.
  • the dimensions of the flow channel are not particularly limited, except by the dimension of the flow plate substrate, as the at least one flow channel must be capable of being contained within the dimensions of the flow plate substrate.
  • the depth of the at least one flow channel, D is less than the thickness, T, of the flow plate substrate. In some embodiments, the depth, D, of the at least one flow channel is equal to the thickness, T, of the flow plate substrate.
  • the depth, D, of the at least one flow channel may be from 0.020 cm to 3 cm, from 0.020 cm to 2 cm, from 0.020 cm to 1 cm, from 0.04 cm to 3 cm, from 0.04 cm to 2 cm, from 0.04 cm to 1 cm, from 0.08 cm to 3 cm, from 0.08 cm to 2 cm, or even from 0.08 cm to 1 cm.
  • the width, W, of the at least one flow channel may be from may be from 0.1 cm to 3 cm, from 0.1 cm to 2 cm, from 0.1 cm to 1 cm, from 0.2 cm to 3 cm, from 0..2 cm to 2 cm, from 0..2 cm to 1 cm, from 0.3 cm to 3 cm, from 0.3 cm to 2 cm, or even from 0.3 cm to 1 cm.
  • the width, W of the at least one flow channel may be from 1 cm to 200 cm, from 1 cm to 150 cm from 1 cm to 100 cm or even from 1 cm to 50 cm.
  • the at least one flow channel may be a serpentine flow channel or it may not be a serpentine flow channel.
  • the size, i.e. dimensions, shape, number (when a plurality of vias are used) and areal density (when a plurality of vias are used) of the at least one via, if present, is not particularly limited.
  • the dimensions of the at least one via are not particularly limited, except by the dimension of the flow plate substrate, as the at least one via must be capable of being contained within the dimensions of the flow plate substrate.
  • the height, H, of the at least one via may be from may be from 0.020 cm to 3 cm, from 0.020 cm to 2 cm, from 0.020 cm to 1 cm, from 0.04 cm to 3 cm, from 0.04 cm to 2 cm, from 0.04 cm to 1 cm, from 0.08 cm to 3 cm, from 0.08 cm to 2 cm, or even from 0.08 cm to 1 cm.
  • the at least one via is a single via, as shown in FIGS, 3 A-3D, for example.
  • the at least one via is a plurality of vias, as shown in FIGS, 1A-1D, for example.
  • the plurality of vias include from 2 to 2000000 vias, from 2 to 100000 vias, from 2 to 10000 vias, from 2 to 1000 vias, from 2 to 500 vias, from 2 to 300 vias, from 2 to 100 vias, from 10 to 2000000 vias, from 10 to 100000 vias , from 10 to 10000 vias, from 10 to 1000 vias, from 10 to 500 vias, from 10 to 300 vias, from 10 to 100 vias, from 25 to 2000000 vias, from 25 to 100000 vias, from 25to 10000 vias, from 25 to 1000 vias, from 25 to 500 vias, from 25 to 300 vias, or even from 25 to 100 vias.
  • the ratio of the surface area of the at least one via (e.g. the sum of the projected surface of a plurality of vias, if a plurality of vias are used) projected onto the surface (first or second major surface) of the flow plate substrate, to the surface area of the flow plate substrate (first or second major surface) is from 0.01 to 0.90, from, 0.01 to 0.80 from 0.01 to 0.70, from 0.05 to 0.90, from, 0.05 to 0.80 from 0.05 to 0.70, from 0.1 to 0.90, from a, 0.1 to 0.80 from 0.1 to 0.70, from 0.2 to 0.90, from, 0.2 to 0.80 from 0.2 to 0.70, from 0.3 to 0.90, from, 0.3 to 0.80 ore even from 0.3 to 0.70.
  • the width of the individual vias, when a plurality of vias are used is from 5 microns to 5 mm, from 5 microns to 2.5 mm, from 5 microns from 1 mm, from 5 microns to 500 microns, from 25 microns to 5 mm, from about 25 microns to 2.5 mm, from 25 microns to 1 mm, from 25 microns to 500 microns, from 50 microns to 5 mm, from 50 microns to 2.5 mm, from 50 microns to 1 mm, from 50 microns to 500 microns, from 100 microns to 5 mm, from 100 microns to 2.5 mm, from 100 microns to 1 mm or even from 5 microns to 100 microns.
  • each individual via may be the same or may vary.
  • the shape of the via may include at least one of a cube, cuboid (rectangular prism), cylinder, triangular prism, hexagonal prism, pyramidal, hemispheroid, pyramidal, truncated pyramidal, conical, truncated conical and the like. Combinations of shapes may be used.
  • the dimensions of the first inlet and outlet ports and second inlet and outlet ports are not particularly limited, except by the dimensions of the flow plate substrate.
  • the inlet and outlet ports enable fluid, e.g. anolyte or catholyte, to access the at least one flow channel.
  • the inlet and outlet ports may supply fluid to more than one flow channel. Multiple fluid inlet and outlet ports may be used.
  • the location of the inlet and outlet ports within the flow plate substrate are selected based on the overall design of the flow plate substrate with respect to its integration into an electrochemical cell or battery.
  • the electrically conductive flow plate substrate may include at least one of a metal, electrically conductive carbon, electrically conductive polymer and electrically conductive polymer composite.
  • Useful metals for the electrically conductive flow plate substrate include, but are not limited to, at least one of silver, copper, gold, aluminum, magnesium, molybdenum, iridium, tungsten, zinc, lead, cobalt, nickel, manganese, ruthenium, lithium, iron, tin, platinum, palladium, tantalum, chromium, antimony, vanadium, titanium, zirconium, bismuth, indium, gallium, and cerium.
  • Noble metals may be particularly useful, due to their stability. Combinations of metal may be used, e.g. metal alloys.
  • the electrically conductive flow plate substrate may be a metal sheet, formed by known techniques.
  • the at least one flow channel and the at least one via, if present, of the electrically conductive flow plate substrate may be formed in the metal sheet using conventional machining techniques discussed previously.
  • the electrically conductive flow plate substrate along with the at least one flow channel and/or the at least one via, if present, of the electrically conductive flow plate substrate may be formed by molding of a liquid metal followed by cooling to solidify the metal.
  • Useful electrically conductive carbon for the electrically conductive flow plate substrate includes, but is not limited to, carbon fiber sheets.
  • the carbon fiber sheets may include an electrically conductive core of a non-carbon fiber material.
  • the carbon fiber sheets may include carbon fiber woven substrates and/or carbon fiber non-woven substrates.
  • the carbon fiber woven substrates and/or carbon fiber non- woven substrates may be polymer-carbon fiber sheet composites or laminates, wherein the carbon fiber sheet is imbibed with a liquid polymer or liquid polymer precursor solution, which is later solidified via cooling or curing, for example, to form a solid polymer-carbon fiber sheet composite.
  • the at least one flow channel and the at least one via, if present, of the electrically conductive flow plate substrate may be formed in the polymer-carbon fiber sheet composites using the previously described conventional machining techniques. Molding techniques may be used to form the at least one flow channel and/or the at least one via, if present, of the polymer-carbon fiber sheet composite during the formation thereof.
  • the polymer of the polymer-carbon fiber sheet composite may include at least one of a thermoplastic and thermoset.
  • the polymer selected for the polymer-carbon fiber sheet composite should have good chemical resistance to the anolyte and/or catholyte to which it will be exposed.
  • Useful electrically conductive polymer for the electrically conductive flow plate substrate includes, but is not limited to, at least one of polyaniline, polypyrrole and polyacetylene.
  • the electrically conductive polymer may be used as a single component or may be used in a dielectric polymer-electrically conductive polymer composite or laminate.
  • Useful electrically conductive polymer composite for the electrically conductive flow plate substrate includes an electrically conductive particulate and a polymer, e.g. a dielectric polymer.
  • the electrically conductive particulate is dispersed in the polymer.
  • the electrically conductive particulate in the electrically conductive polymer composite enables the composite to be electrically conductive, particularly when the polymer is a dielectric polymer.
  • the amount of electrically conductive particulate required to make the electrically conductive polymer composite electrically conductive depends on the particulate type and the material comprising the electrically conductive particulate.
  • High aspect ratio electrically conductive particulate e.g.
  • electrically conductive fiber may require a lower amount of particulate to form an electrically conductive composite compared to a low aspect ratio particulate, e.g. an electrically conductive spherical particle.
  • a particulate comprising a highly electrically conductive material, e.g. silver, may require a lower amount of particulate to form an electrically conductive composite compared to a less electrically conductive material, e.g. iron.
  • the amount of electrically conductive particulate in the electrically conductive polymer composite may be between 5 percent by weight and 95 percent by weight, between 15 percent by weight and 95 percent by weight, between 25 percent by weight and 95 percent by weight, between 5 percent by weight and 85 percent by weight, between 15 percent by weight and 85 percent by weight, between 25 percent by weight and 85 percent by weight, between 5 percent by weight and 75 percent by weight, between 15 percent by weight and 75 percent by weight, or even between 25 percent by weight and 75 percent by weight.
  • the amount of polymer in the electrically conductive polymer composite may be between 5 percent by weight and 95 percent by weight, between 5 percent by weight and 85 percent by weight, between 5 percent by weight and 75 percent by weight, between 15 percent by weight and 95 percent by weight, between 15 percent by weight and 85 percent by weight, between 15 percent by weight and 75 percent by weight, between 25 percent by weight and 95 percent by weight, between 25 percent by weight and 85 percent by weight, or even between 25 percent by weight and 75 percent by weight.
  • the electrically conductive particulate may include at least one of a metal particulate, electrically conductive carbon particulate and electrically conductive polymer particulate.
  • the metal of the metal particulate may include, but is not limited to at least one of silver, copper, gold, aluminum, magnesium, molybdenum, iridium, tungsten, zinc, lead, cobalt, nickel, manganese, ruthenium, lithium, iron, tin, platinum, palladium, tantalum, chromium, antimony, vanadium, titanium, zirconium, bismuth, indium, gallium, and cerium.
  • Noble metals may be particularly useful, due to their stability. Combinations of metal may be used, e.g. metal alloys.
  • the electrically conductive carbon particulate may include, but is not limited to, at least one of carbon particles, carbon flakes, carbon fibers, carbon dendrites, carbon nanotubes and branched carbon nanotubes; combinations may be used. In some embodiments, the electrically conductive carbon particulate may include at least one of graphite particles, graphite flakes, graphite fibers and graphite dendrites; combinations may be used.
  • the electrically conductive polymer particulate includes, but is not limited to, at least one of polyaniline, polypyrrole and polyacetylene.
  • the term "particulate”, is meant to include particles, flakes, fibers, dendrites and the like.
  • Particulate particles generally include particulates that have aspect ratios of length to width and length to thickness both of which are between 1 and 5.
  • the particle size may be from between 0.001 microns to 100 microns, from between 0.001 microns to 50 microns, from between 0.001 to 25 microns, from between 0.001 microns to 10 microns, from 0.001 microns to 1 microns, from between 0.01 microns and 100 microns, from between 0.01 microns to 50 microns, from between 0.01 to 25 microns, from between 0.01 microns to 10 microns, from 0.01 microns to 1 microns, from between 0.05 microns to 100 microns, from between 0.05 microns to 50 microns, from between 0.05 to 25 microns, from between 0.05 microns to 10 microns, from 0.05 microns to
  • Particulate flakes generally include particulates that have a length and a width each of which is significantly greater than the thickness of the flake.
  • a flake includes particulates that have aspect ratios of length to thickness and width to thickness each of which is greater than 5.
  • the length and width of the flake may each be from between 0.001 microns to 50 microns, from between 0.001 to 25 microns, from between 0.001 microns to 10 microns, from 0.001 microns to 1 microns, from between 0.01 microns to 50 microns, from between 0.01 to 25 microns, from between 0.01 microns to 10 microns, from 0.01 microns to 1 microns, from between 0.05 microns to 50 microns, from between 0.05 to 25 microns, from between 0.05 microns to 10 microns, from 0.05 microns to 1 microns, from between 0.1 microns to 50 microns, from between 0.1 to 25 microns, from between 0.1 microns to 10 microns, or even from between 0.1 microns to 1 microns. Flakes may be platelet in shape.
  • Particulate dendrites include particulates having a branched structure.
  • the particle size of the dendrites may be the same as those disclosed for the particulate particles, discussed above.
  • Particulate fibers generally include particulates that have aspect ratios of the length to width and length to thickness both of which are greater 10 and a width to thickness aspect ratio less than 5.
  • aspect ratios of the length to width and length to thickness both of which are greater 10 and a width to thickness aspect ratio less than 5.
  • the width and thickness would be the same and would be equal to the diameter of the circular cross-section.
  • Both the length to thickness and length to width aspect ratios of the fiber may be between 10 and 1000000, between 10 and 100000, between 10 and 1000, between 10 and 500, between 10 and 250, between 10 and 100, between 10 and 50, between 20 and 1000000, between 20 and 100000, between 20 and 1000, between 20 and 500, between 20 and 250, between 20 and 100 or even between 20 and 50.
  • the width and thickness of the fiber may each be from between 0.001 to 100 microns, from between 0.001 microns to 50 microns, from between 0.001 to 25 microns, from between 0.001 microns to 10 microns, from 0.001 microns to 1 microns, from between 0.01 to 100 microns, from between 0.01 microns to 50 microns, from between 0.01 to 25 microns, from between 0.01 microns to 10 microns, from 0.01 microns to 1 microns, from between 0.05 to 100 microns, from between 0.05 microns to 50 microns, from between 0.05 to 25 microns, from between 0.05 microns to 10 microns, from 0.05 microns to 1 microns, from between 0.1 to 100 microns, from between 0.1 microns to 50 microns, from between 0.1 to 25 microns, from between 0.1 microns to 10 microns, or even from between 0.1 microns to 1 microns.
  • the polymer of the polymer-carbon fiber sheet composite and the polymer of the electrically conductive polymer composite is not particularly limited. However, in order to ensure long term stability of the polymer in the anolyte and/or catholyte liquids it may be exposed to during use, the polymer may be selected to have good chemical resistance to the anolyte and/or catholyte, including the associated solvent, oxidizing/reducing active species, salts and/or other additives included therein.
  • the polymer may include at least one of a thermoplastic and thermoset.
  • the polymer may include a thermoplastic.
  • the polymer may include a thermoset.
  • the polymer may consists essentially of a thermoplastic.
  • the polymer may consists essentially of a thermoset.
  • Thermoplastics may include thermoplastic elastomers.
  • a thermoset may include a B-stage thermoset, e.g. a B- stage thermoset after final cure.
  • the polymer may include at least one of a thermoplastic and a B-stage thermoset.
  • the polymer may consist essentially of a B-stage thermoset, e.g. a B-stage thermoset after final cure.
  • polymer includes, but is not limited to, at least one of epoxy resin, phenolic resin, ionic polymer, polyurethane, urea-formadehyde resin, melamine resin, polyester, e.g. polyethylene terephthalate, polyamide, polyether, polycarbonate, polyimide, polysulphone, polyphenylene oxide, polyacrylate, polymethacrylate, polyolefin, e.g.
  • polyethylene and polypropylene polyethylene and polypropylene
  • styrene and styrene based random and block copolymer e.g. styrene-butadiene- styrene
  • chlorinated polymer e.g. polyvinyl chloride
  • fluorinated polymer e.g. polyvinylidene fluoride and polytetrafluoroethylene.
  • the polymer may be at least one of polyurethane, polyester, polyamide, polyether, polycarbonate, polyimide, polysulphone, polyphenylene oxide, polyacrylate, polymethacrylate, polyolefin, styrene and styrene based random and block copolymer, chlorinated polymer, and fluorinated polymer.
  • the polymer may be a polymer blend.
  • the polymer blend may include at least two polymers selected from the polymers of the present disclosure.
  • the polymer-carbon fiber sheet composite and/or the electrically conductive polymer composite may include non-electrically conductive inorganic material, e.g. and non-electrically conductive inorganic filler, e.g. a metal oxide such as silica, alumina, zirconia and the like and combinations thereof.
  • non-electrically conductive inorganic filler e.g. a metal oxide such as silica, alumina, zirconia and the like and combinations thereof.
  • polymer-carbon fiber sheet composite and the electrically conductive polymer composite includes from 0.5 percent to 20 percent, from 0.5 percent to 15 percent, from 0.5 percent to 10 percent, or even from 0.5 percent to 5 percent by weight non-electrically conductive inorganic filler.
  • Non-electrically conductive inorganic filler may be used to improve various mechanical properties, e.g. tensile strength, toughness and/or flexing or bending strength.
  • the polymer of the polymer-carbon fiber sheet composite and/or the electrically conductive polymer composite has a softening temperature from 50 degrees centigrade to 400 degrees centigrade, from 50 degrees centigrade to 350 degrees centigrade, from 50 degrees centigrade to 300 degrees centigrade or even from 50 degrees centigrade to 250 degrees centigrade. In some embodiments, the polymer of the polymer- carbon fiber sheet composite and/or the electrically conductive polymer composite is non- tacky at 25 degrees centigrade, 30 degrees centigrade, 40 degree centigrade, or even 50 degrees centigrade.
  • the polymer of the polymer-carbon fiber sheet composite and/or the electrically conductive polymer composite contains from 0 percent to 15 percent by weight, from 0 percent to 10 percent by weight, from 0 percent to 5 percent by weight, from 0 percent to 3 percent by weight, from 0 percent to 1 percent by weight or even substantially 0 percent by weight pressure sensitive adhesive.
  • Low modulus and/or highly viscoelastic materials, such as a pressure sensitive adhesive may flow during use, due to the compression forces within an electrochemical cell or liquid flow battery, and may make it difficult to obtain the desired separation between cell or battery components.
  • the modulus, e.g. Young's modulus, of the polymer of the polymer-carbon fiber sheet composite and/or the electrically conductive polymer composite may be from 0.010
  • GPa to 10 GPa from 0.1 GPa to 10 GPa, from 0.5 GPa to 10 GPa, from 0.010 GPa to 5 GPa, from 0.1 GPa to 5 GPa or even from 0.5 GPa to 5 GPa.
  • Dielectric flow plate substrate i.e. a non-electrically conductive flow plate substrate, may include at least one of a dielectric polymer and a dielectric inorganic material.
  • the dielectric flow plate substrate includes at least one dielectric polymer.
  • Dielectric polymer may be particularly useful, due to at least one of low cost, low weight and ease of processing.
  • Useful dielectric inorganic material include, but is not limited to, metal oxides.
  • the metal oxides of the dielectric inorganic material include, but are not limited to at least one of silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, cerium oxide, and the like.
  • the amount of dielectric inorganic material in the dielectric flow plate substrate may be between 15 percent by weight and 100 percent by weight, between 25 percent by weight and 100 percent by weight, between 35 percent by weight and 100 percent by weight, between 50 percent by weight and 100 percent by weight, between 70 percent by weight and 100 percent by weight, between 85 percent by weight and 100 percent by weight, or even between 90 percent by weight and 100 percent by weight.
  • the dielectric polymer of the dielectric flow plate substrate is not particularly limited. However, in order to ensure long term stability of the dielectric polymer in the anolyte and/or catholyte liquids it may be exposed to during use, the dielectric polymer may be selected to have good chemical resistance to the anolyte and/or catholyte, including the associated solvent, oxidizing/reducing active species, salts and/or other additives included therein. In some embodiments, the dielectric polymer may include at least one of a dielectric
  • the dielectric polymer may include a dielectric thermoplastic. In some embodiments, the dielectric polymer may include a dielectric thermoset. In some embodiments, the dielectric polymer may consists essentially of a dielectric thermoplastic. Dielectric thermoplastics may include dielectric thermoplastic elastomers. In some embodiments, the dielectric polymer may consists essentially of a dielectric thermoset. A dielectric thermoset may include a B-stage dielectric thermoset, e.g. a B-stage dielectric thermoset after final cure. In some embodiments, the dielectric polymer (dielectric polymer type) may include at least one of a dielectric thermoplastic and a B-stage dielectric thermoset.
  • the dielectric polymer may consist essentially of a B-stage dielectric thermoset, e.g. a B-stage dielectric thermoset after final cure.
  • dielectric polymer includes, but is not limited to, at least one of epoxy resin, phenolic resin, ionic polymer, polyurethane, urea-formadehyde resin, melamine resin, polyester, e.g. polyethylene terephthalate, polyamide, polyether, polycarbonate, polyimide, polysulphone, polyphenylene oxide, polyacrylate, polymethacrylate, polyolefin, e.g.
  • the dielectric polymer may be at least one of polyurethane, polyester, polyamide, polyether, polycarbonate, polyimide, polysulphone, polyphenylene oxide, polyacrylate,
  • the dielectric polymer may be a dielectric polymer blend or dielectric polymer composite.
  • the dielectric polymer blend and/or composite may include at least two dielectric polymers selected from the dielectric polymers of the present disclosure.
  • the amount of dielectric polymer in the dielectric flow plate substrate may be between 15 percent by weight and 100 percent by weight, between 25 percent by weight and 100 percent by weight, between 35 percent by weight and 100 percent by weight, between 50 percent by weight and 100 percent by weight, between 70 percent by weight and 100 percent by weight, between 85 percent by weight and 100 percent by weight, or even between 90 percent by weight and 100 percent by weight.
  • the dielectric polymer may contain other fillers, e.g. inorganic materials, including but not limited to inorganic metal oxides.
  • the dielectric polymer may even include small amounts; less than 5 percent by weight, less than 4 percent by weight, less than 3 percent by weight, less than 2 percent by weight or even less than 1 percent by weight; of electrically conductive material, so long as the addition of the electrically conductive material does not significantly alter the dielectric property of the dielectric polymer.
  • the dielectric polymer of the dielectric flow plate substrate has a softening temperature from 50 degrees centigrade to 400 degrees centigrade, from 50 degrees centigrade to 350 degrees centigrade, from 50 degrees centigrade to 300 degrees centigrade or even from 50 degrees centigrade to 250 degrees centigrade. In some
  • the modulus, e.g. Young's modulus, of the dielectric polymer may be from 0.010 GPa to 10 GPa, from 0.1 GPa to 10 GPa, from 0.5 GPa to 10 GPa, from 0.010 GPa to 5 GPa, from 0.1 GPa to 5 GPa, from 0.5 GPa to 5 GPa, from 0.010 GPa to 3 GPa, from 0.1 GPa to 3 GPa, or even from 0.5 GPa to 3 GPa.
  • the porous electrode material of the present disclosure is electrically conductive and the porosity facilitates the oxidation/reduction reaction that occur therein by increasing the amount of active surface area for reaction to occur, per unit volume of electrode, and by allowing the anolyte and catholyte to permeate into the porous regions and access this additional surface area.
  • the porous electrode material and/or the electrically conductive material may include at least one of woven and nonwoven fiber mats, woven and nonwoven fiber papers, felts and cloths (fabrics).
  • the porous electrode material and/or the electrically conductive material includes carbon fiber.
  • the carbon fiber may include, but is not limited to, glass like carbon, amorphous carbon, graphite, graphene, carbon nanotubes and graphite.
  • Particularly useful porous electrode material and/or the electrically conductive material include carbon papers, carbon felts and carbon cloths (fabrics), e.g. graphite papers, graphite felts and graphite cloths.
  • the porous electrode material and/or the electrically conductive material includes at least one of carbon paper, carbon felt and carbon cloth.
  • the porous electrode material and/or the electrically conductive material may include at least one of a metal film, an electrically conductive particulate and an electrically conductive polymer composite; the electrically conductive polymer composite may include polymer and the electrically conductive particulate.
  • the electrically conductive particulate may include at least one of metal particulate, electrically conductive carbon particulate and electrically conductive polymer particulate.
  • the porous electrode material and/or the electrically conductive material includes a metal material, e.g. a porous metal material.
  • the metal material may be a metal film.
  • the metal of the metal material may include, but is not limited to, at least one of silver, copper, gold, aluminum, magnesium, molybdenum, iridium, tungsten, zinc, lead, cobalt, nickel, manganese, ruthenium, lithium, iron, tin, platinum, palladium, tantalum, chromium, antimony, vanadium, titanium, zirconium, bismuth, indium, gallium, and cerium.
  • Combinations of metal may be used, e.g. metal alloys.
  • Noble metals may be particularly useful, due to their stability.
  • the porous electrode material and/or the electrically conductive material includes electrically conductive particulate, e.g. electrically conductive carbon particulate. In some embodiments, the porous electrode material and/or the electrically conductive material includes from 30 percent to 100 percent, from 40 percent to 100 percent, from 50 percent to 100 percent, from 60 percent to 100 percent, from 70 percent to 100 percent, from 80 percent to 100 percent, from 90 percent to 100 percent or even from 95 percent to 100 percent carbon fiber by weight.
  • the porous electrode material and/or the electrically conductive material includes from 50 percent to 100 percent, from 60 percent to 100 percent, from 70 percent to 100 percent, from 80 percent to 100 percent, from 90 percent to 100 percent, from 95 percent to 100 percent or even from 97 percent to 100 percent electrically conductive particulate by weight.
  • the electrically conductive particulate of the porous electrode material and/or the electrically conductive material may include at least one of a metal particulate, electrically conductive carbon particulate and electrically conductive polymer particulate.
  • the metal of the metal particulate may include, but is not limited to, at least one of silver, copper, gold, aluminum, magnesium, molybdenum, iridium, tungsten, zinc, lead, cobalt, nickel, manganese, ruthenium, lithium, iron, tin, platinum, palladium, tantalum, chromium, antimony, vanadium, titanium, zirconium, bismuth, indium, gallium, and cerium.
  • the electrically conductive carbon particulate may include, but is not limited to, at least one of carbon particles, carbon flakes, carbon fibers, carbon dendrites, carbon nanotubes and branched carbon nanotubes; combinations may be used. In some embodiments, the electrically conductive carbon particulate may include at least one of graphite particles, graphite flakes, graphite fibers and graphite dendrites; combinations may be used.
  • the porous electrode material and/or the electrically conductive material includes from 5 percent to 100 percent, from 10 percent to 100 percent, from 20 percent to 100 percent, from 35 percent to 100 percent or even from 50 percent to 100 percent, by weight, of at least one of graphite particles, graphite flakes, graphite fibers and graphite dendrites.
  • the electrically conductive polymer particulate includes, but is not limited to, at least one of polyaniline, polypyrrole and polyacetylene. Combinations of electrically conductive polymer particulate may be used.
  • the amount of electrically conductive polymer particulate in the porous electrode material and/or the electrically conductive material may be from 5 to 99 percent, from 5 to 95 percent, from 5 to 90 percent, from 5 to 80 percent, from 5 to 70 percent, from 10 to 99 percent, from 10 to 95 percent, from 10 to 90 percent, from 10 to 80 percent, from 10 to 70 percent, from 25 to 99 percent, from 25 to 95 percent, from 25 to 90 percent, from 25 to 80 percent, or even from 5 to 70 percent by weight.
  • the porous electrode material and/or the electrically conductive material include an electrically conductive polymer composite comprising at least one polymer and at least one electrically conductive particulate, the at least one electrically conductive particulate may include electrically conductive particulate as described above.
  • the polymer may include at least one of a thermoplastic polymer and a thermoset polymer.
  • the polymer of the porous electrode material and/or the electrically conductive material may be at least one of a polymer particulate and polymer binder resin.
  • the polymeric particulate may be at least one of polymer particles, polymer flakes, polymer fibers and polymer dendrites.
  • the polymer is fused polymer particulate.
  • Fused polymer particulate may be formed from polymer particulates that are brought to a temperature to allow the contact surfaces of adjacent polymer particulates to fuse together. After fusing the individual particulates that formed the fused polymer particulate can still be identified. A fused polymer particulate is porous.
  • Fused polymer particulate is not particulate that has been completely melted to form a solid substrate, i.e. a non-porous substrate.
  • the polymer particulate may be fused at a temperature that is not less than 30 degrees centigrade, not less than 20 degrees centigrade or even not less than 10 degrees centigrade lower than the lowest glass lowest transition temperature of the polymer particulate.
  • the polymer particulate may have more than one glass transition temperatures, if, for example, it is a block copolymer or a core-shell polymer.
  • the polymer particulate may be fused at a temperature that is below the highest melting temperature of the polymer particulate or, when the polymer particulate is an amorphous polymer, no greater than 50 degrees centigrade, no greater than 30 degrees centigrade or even no greater than 10 degrees centigrade above the highest glass transition temperature of the polymer particulate.
  • the polymer of the porous electrode material and/or the electrically conductive material may include a polymer binder resin and the polymer binder resin may be derived from a polymer precursor liquid.
  • a polymer precursor liquid may be at least one of a polymer solution and a reactive polymer precursor liquid, each capable of being at least one of polymerized, cured, dried and fused to form a polymer binder resin.
  • a polymer solution may include at least one polymer dissolved in at least one solvent.
  • a polymer solution may be capable of being at least one of polymerized, cured, dried and fused to form a polymer binder resin. In some embodiments, the polymer solution is dried to form a polymer binder resin.
  • a reactive polymer precursor liquid includes at least one of liquid monomer and liquid oligomer.
  • the monomer may be a single monomer or may be a mixture of at least two different monomers.
  • the oligomer may be a single oligomer or a mixture at least two different oligomers. Mixtures of one or more monomers and one or more oligomers may also be used.
  • the reactive polymer precursor liquid may include at least one, optional, solvent.
  • the reactive polymer precursor liquid may include at least one, optional, polymer, which is soluble in the liquid components of the reactive polymer precursor liquid.
  • the reactive polymer precursor liquid may be capable of being at least one of polymerized, cured, dried and fused to form a polymer binder resin.
  • the reactive polymer precursor liquid is cured to form a polymer binder resin. In some embodiments, the reactive polymer precursor liquid is polymerized to form a polymer binder resin. In some embodiments, the reactive polymer precursor liquid is cured and polymerized to form a polymer binder resin.
  • the terms "cure”, “curing”, “cured” and the like are used herein to refer to a reactive polymer precursor liquid that is increasing its molecular weight through one or more reactions that include at least one crosslinking reaction. Generally, curing leads to a thermoset material that may be insoluble in solvents.
  • polymerize generally refer to a reactive polymer precursor liquid that is increasing its molecular weight through one or more reactions that do not include a crosslinking reaction.
  • polymerization leads to a thermoplastic material that may be soluble in an appropriate solvent.
  • a reactive polymer precursor liquid that is reacting by at least one crosslinking reaction and at least one polymerization reaction may form either a thermoset or thermoplastic material, depending on the degree of polymerization achieved and the amounted crosslinking of the final polymer.
  • Monomers and/or oligomers useful in the preparation of a reactive polymer precursor liquid include, but are not limited to, monomers and oligomers conventionally used to form the polymers, e.g. thermosets, thermoplastics and thermoplastic elastomers, described herein
  • Polymers useful in the preparation of a polymer solution include, but are not limited to the thermoplastic and thermoplastic elastomer polymers described herein (below).
  • the electrically conductive particulate e.g. electrically conductive carbon particulate
  • the electrically conductive particulate may be adhered to the polymer, polymer particulate and/or polymer binder resin.
  • the electrically conductive particulate e.g. electrically conductive carbon particulate
  • the electrically conductive particulate may be adhered to the surface of the polymer particulate.
  • the electrically conductive particulate may be adhered to the surface of the fused polymer particulate.
  • the polymer of the porous electrode material and/or the electrically conductive material may be selected to facilitate the transfer of select ion(s) of the electrolytes through at least one of the porous electrode material and the electrically conductive material. This may be achieved by allowing the electrolyte to easily wet a given polymer.
  • the material properties, particularly the surface wetting characteristics of the polymer may be selected based on the type of anolyte and catholyte solution, i.e. whether they are aqueous based or non-aqueous based. As disclosed herein, an aqueous based solution is defined as a solution wherein the solvent includes at least 50% water by weight.
  • a non-aqueous base solution is defined as a solution wherein the solvent contains less than 50% water by weight.
  • the polymer of the porous electrode material and/or the electrically conductive material may be hydrophilic. This may be particularly beneficial when the porous electrode material and/or the electrically conductive material is to be used in conjunction with aqueous anolyte and/or catholyte solutions.
  • the polymer may have a surface contact angle with water, catholyte and/or anolyte of less than 90 degrees.
  • the polymer may have a surface contact with water, catholyte and/or anolyte of between 85 degrees and 0 degrees, between 70 degrees and 0 degrees, between 50 degrees and 0 degrees, between 30 degrees and 0 degrees, between 20 degrees and 0 degrees, or even between 10 degrees and 0 degrees.
  • Polymer (polymer type) of the porous electrode material and/or the electrically conductive material which may be a polymer particulate or a polymer binder resin, may include thermoplastic resins (including thermoplastic elastomer), thermoset resins (including glassy and rubbery materials) and combinations thereof.
  • Useful thermoplastic resins include, but are not limited to, homopolymer, copolymer and blends of at least one of polyalkylene, e.g. polyethylene, high molecular weight polyethylene, high density polyethylene, ultra-high molecular weight polyethylene, polypropylene, high molecular weight polypropylene;
  • polyacrylate polymethacrylate, styrene and styrene based random and block copolymer, e.g. styrene-butadiene-styrene; polyester, e.g. polyethylene terephtahalate; polycarbonate, polyamide, polyamide-amine; polyalkylene glycol, e.g. polyethylene glycol and
  • thermoset resins include, but are not limited to, homopolymer, copolymer and/or blends of at least one of epoxy resin, phenolic resin, polyurethanes, urea- formadehyde resin and melamine resin.
  • the polymer of the porous electrode material and/or the electrically conductive material has a softening temperature, e.g. the glass transition temperature and/or the melting temperature of between 20 degrees centigrade and 400 degrees centigrade, between 20 degrees centigrade and 300 degrees centigrade, between 20 degrees centigrade and 200 degrees centigrade, between 35 degrees centigrade and 400 degrees centigrade, between 35 degrees centigrade and 300 degrees centigrade, between 35 degrees centigrade and 200 degrees centigrade, between 50 degrees centigrade and 400 degrees centigrade, between 50 degrees centigrade and 300 degrees centigrade, between 50 degrees centigrade and 200 degrees centigrade, between 75 degrees centigrade and 400 degrees centigrade, between 75 degrees centigrade and 300 degrees centigrade, or even between 75 degrees centigrade and 200 degrees centigrade.
  • a softening temperature e.g. the glass transition temperature and/or the melting temperature of between 20 degrees centigrade and 400 degrees centigrade, between 20 degrees centigrade and 300 degrees centigrade, between 20 degrees cent
  • the polymer particulate is composed of two or more polymers and has a core-shell structure, i.e. an inner core comprising a first polymer and an outer shell comprising a second polymer.
  • the polymer of the outer shell e.g. second polymer
  • has a softening temperature e.g. the glass transition temperature and/or the melting temperature that is lower than softening temperature of the first polymer.
  • the second polymer has a softening temperature, e.g.
  • the glass transition temperature and/or the melting temperature of between 20 degrees centigrade and 400 degrees centigrade between 20 degrees centigrade and 300 degrees centigrade, between 20 degrees centigrade and 200 degrees centigrade, between 35 degrees centigrade and 400 degrees centigrade, between 35 degrees centigrade and 300 degrees centigrade, between 35 degrees centigrade and 200 degrees centigrade, between 50 degrees centigrade and 400 degrees centigrade, between 50 degrees centigrade and 300 degrees centigrade, between 50 degrees centigrade and 200 degrees centigrade, between 75 degrees centigrade and 400 degrees centigrade, between 75 degrees centigrade and 300 degrees centigrade, or even between 75 degrees centigrade and 200 degrees centigrade.
  • the polymer of the porous electrode material and/or the electrically conductive material may be an ionic polymer or non-ionic polymer.
  • Ionic polymer include polymer wherein a fraction of the repeat units are electrically neutral and a fraction of the repeat units have an ionic functional group, i.e. an ionic repeat unit.
  • the polymer is an ionic polymer, wherein the ionic polymer has a mole fraction of repeat units having an ionic functional group of between 0.005 and 1.
  • the polymer is a non- ionic polymer, wherein the non-ionic polymer has a mole fraction of repeat units having an ionic functional group of from less than 0.005 to 0.
  • the polymer is a non-ionic polymer, wherein the non-ionic polymer has no repeat units having an ionic functional group. In some embodiments, the polymer consists essentially of an ionic polymer. In some embodiments, the polymer consists essentially of a non-ionic polymer.
  • Ionic polymer includes, but is not limited to, ion exchange resins, ionomer resins and combinations thereof. Ion exchange resins may be particularly useful.
  • ionic resin include resin wherein a fraction of the repeat units are electrically neutral and a fraction of the repeat units have an ionic functional group.
  • the ionic resin has a mole fraction of repeat units with ionic functional groups between 0.005 and 1.
  • the ionic resin is a cationic resin, i.e. its ionic functional groups are negatively charged and facilitate the transfer of cations, e.g.
  • the cationic resin is a proton cationic resin.
  • the ionic resin is an anionic exchange resin, i.e. its ionic functional groups are positively charged and facilitate the transfer of anions.
  • the ionic functional group of the ionic resin may include, but is not limited, to carboxylate, sulphonate, sulfonamide, quaternary ammonium, thiuronium, guanidinium, imidazolium and pyridinium groups.
  • Combinations of ionic functional groups may be used in an ionic resin.
  • Ionomer resin include resin wherein a fraction of the repeat units are electrically neutral and a fraction of the repeat units have an ionic functional group.
  • an ionomer resin will be considered to be a resin having a mole fraction of repeat units having ionic functional groups of no greater than 0.15.
  • the ionomer resin has a mole fraction of repeat units having ionic functional groups of between 0.005 and 0.15, between 0.01 and 0.15 or even between 0.3 and 0.15.
  • the ionomer resin is insoluble in at least one of the anolyte and catholyte.
  • the ionic functional group of the ionomer resin may include, but is not limited, to carboxylate, sulphonate, sulfonamide, quaternary ammonium, thiuronium, guanidinium, imidazolium and pyridinium groups. Combinations of ionic functional groups may be used in an ionomer resin. Mixtures of ionomer resins may be used.
  • the ionomers resin may be a cationic resin or an anionic resin.
  • Useful ionomer resin include, but are not limited to NAFION, available from DuPont, Wilmington, Delaware; AQUIVION, a perfluorosulfonic acid, available from SOLVAY, Brussels, Belgium; FLEMION and SELEMION, fluoropolomer ion exchange resin, from Asahi Glass, Tokyo, Japan; FUMASEP ion exchange resin, including FKS, FKB, FKL, FKE cation exchange resins and FAB, FAA, FAP and FAD anionic exchange resins, available from Fumatek, Bietigheim-Bissingen, Germany, polybenzimidazols, and ion exchange materials and membranes described in U.S. Pat. No. 7,348,088, incorporated herein by reference in its entirety.
  • Ion exchange resin include resin wherein a fraction of the repeat units are electrically neutral and a fraction of the repeat units have an ionic functional group.
  • an ion exchange resin will be considered to be a resin having a mole fraction of repeat units having ionic functional groups of greater than 0.15 and less than 1.00.
  • the ion exchange resin has a mole fraction of repeat units having ionic functional groups of greater than 0.15 and less than 0.90, greater than 0.15 and less than 0.80, greater than 0.15 and less than 0.70, greater than 0.30 and less than 0.90, greater than 0.30 and less than 0.80, greater than 0.30 and less than 0.70 greater than 0.45 and less than 0.90, greater than 0.45 and less than 0.80, and even greater than 0.45 and less than 0.70.
  • the ion exchange resin may be a cationic exchange resin or may be an anionic exchange resin.
  • the ion exchange resin may, optionally, be a proton ion exchange resin.
  • the type of ion exchange resin may be selected based on the type of ion that needs to be transported between the anolyte and catholyte through the ion permeable membrane.
  • the ion exchange resin is insoluble in at least one of the anolyte and catholyte.
  • the ionic functional group of the ion exchange resin may include, but is not limited, to carboxylate, sulphonate, sulfonamide, quaternary ammonium, thiuronium, guanidinium, imidazolium and pyridinium groups.
  • Combinations of ionic functional groups may be used in an ion exchange resin.
  • Mixtures of ion exchange resins resin may be used.
  • Useful ion exchange resins include, but are not limited to, fluorinated ion exchange resins, e.g. perfluorosulfonic acid copolymer and perfluorosulfonimide copolymer, a sulfonated polysulfone, a polymer or copolymer containing quaternary ammonium groups, a polymer or copolymer containing at least one of guanidinium or thiuronium groups a polymer or copolymer containing imidazolium groups, a polymer or copolymer containing pyridinium groups.
  • the polymer may be a mixture of ionomer resin and ion exchange resin.
  • the amount of polymer contained in the of the porous electrode material and/or the electrically conductive material, on a weight basis may be from 1 to 95 percent, from 5 to 95 percent, from 10 to 95 percent, from 20 to 95 percent, from 30 to 95 percent, from 1 to 90 percent, from 5 to 90 percent, from 10 to 90 percent, from 20 to 90 percent, from 30 to 90 percent, from 1 to 75 percent, from 5 to 75 percent, from 10 to 75 percent, from 20 to 75 percent, from 30 to 75 percent, from 1 to 70 percent, from 5 to 70 percent, from 10 to 70 percent, from 20 to 70 percent, from 30 to 70 percent, from 1 to 60 percent, from 5 to 60, from 10 to 60 percent, from 20 to 60 percent, from 30 to 60 percent, from 1 to 50 percent, from 5 to 50 percent, from 10 to 50 percent, from 20 to 50 percent, from 30 to 50 percent, from 1 to 40 percent, from 5 to 40 percent, from 10 to 40 percent, from 20 to 40 percent, or even from 30 to 40 percent.
  • the porous electrode material and/or the electrically conductive material of the present disclosure may include non-electrically conductive, inorganic particulate, e.g. non- electrically conductive inorganic filler.
  • non-electrically conductive inorganic filler includes, but is not limited to, metal oxide such as silica, alumina, zirconia and the like and
  • the porous electrode material and/or the electrically conductive material includes from 0.5 percent to 20 percent, from 0.5 percent to 15 percent, from 0.5 percent to 10 percent, or even from 0.5 percent to 5 percent by weight non-electrically conductive inorganic filler.
  • Non-electrically conductive inorganic filler may be used to improve various mechanical properties, e.g. tensile strength, toughness and/or flexing or bending strength
  • the polymer and electrically conductive particulate are fabricated into the porous electrode material and/or the electrically conductive material by mixing the polymer and electrically conductive particulate to form an electrically conductive blend, coating the electrically conductive blend into the at least one flow channel of the flow plate substrate (with respect to the porous electrode material) or coating the electrically conductive blend into the at least one via (with respect to the electrically conductive material), and providing at least one of a fusing, curing, polymerizing and drying treatment to form porous electrode material and/or an electrically conductive material.
  • the porous electrode material and/or the electrically conductive material may be in the form of a continuous sheet or layer.
  • the temperature may be such that the temperature is near, at or above the softening temperature of the polymer, e.g. the glass transition temperature and/or the melting temperature of the polymer, which may aid in the adhering of electrically conductive particulate to the polymer and/or further fuse the polymer.
  • the processing of the polymer and electrically conductive particulate blend may be modified by those of ordinary skill in the art to produce a final material that is porous or non-porous.
  • the electrically conductive material is contained in at least a portion of the at least one via, if present. In some embodiments, 20 to 100 percent, 30 to 100 percent, 40 to 100 percent, 50 to 100 percent, 60 to 100 percent, 70 to 100 percent, 80 to 100 percent, 90 to 100 percent or even from 95 to 100 percent of the volume of the at least one via contains electrically conductive material. Enhanced electrical performance (e.g. greater electrical conductivity and/or lower electrical resistance) may be obtained when 50 to 100 percent, 60 to 100 percent, 70 to 100 percent, 80 to 100 percent, 90 to 100 percent or even from 95 to 100 percent of the volume of the at least one via contains electrically conductive material.
  • the volume of the at least one via is an inherent property of the at least one via and the volume is based on the dimensions and number of the at least one via.
  • the porous electrode material is contained in at least a portion of the at least one flow channel of the flow plate substrate. In some embodiments, 20 to 100 percent, 30 to 100 percent, 40 to 100 percent, 50 to 100 percent, 60 to 100 percent, 70 to 100 percent, 80 to 100 percent, 90 to 100 percent or even from 95 to 100 percent of the volume of the at least one flow channel contains porous electrode material. Enhanced electrical performance (e.g. greater electrical conductivity and/or lower electrical resistance) may be obtained when 50 to 100 percent, 60 to 100 percent, 70 to 100 percent, 80 to 100 percent, 90 to 100 percent or even from 95 to 100 percent of the volume of the at least one flow channel contains porous electrode material.
  • Enhanced electrical performance e.g. greater electrical conductivity and/or lower electrical resistance
  • the volume of the at least one flow channel is an inherent property of the at least one flow channel and the volume is based on the dimensions and number of the at least one flow channel.
  • the electrically conductive material includes at least one of an electrically conductive sheet, an electrically conductive pin and a plurality of electrically conductive pins.
  • the electrically conductive material may be a solid electrically conductive material, i.e. impervious to fluid flow.
  • the electrically conductive material includes at least one of metal sheet, a metal pin and a plurality of metal pins.
  • the metal of the at least one of metal sheet, a metal pin and a plurality of metal pins may include at least one of silver, copper, gold, aluminum, magnesium, molybdenum, iridium, tungsten, zinc, lead, cobalt, nickel, manganese, ruthenium, lithium, iron, tin, platinum, palladium, tantalum, chromium, antimony, vanadium, titanium, zirconium, bismuth, indium, gallium, and cerium.
  • Noble metals may be particularly useful, due to their stability.
  • the electrically conductive material includes from 70 to 100 percent, from 80 to 100, from 90 to 100 percent, from 95 to 100 percent, from 98 to 100 percent or even from 99 to 100 percent by weight metal. In some embodiments, the electrically conductive material is 100 percent metal by weight. In some embodiments, the electrically conductive material contains less than 20 percent, less than 10 percent, less than 5 percent, less than 1 percent or even 0 percent voids, based on volume.
  • polymer particulate and electrically conductive particulate may be mixed together as dry components, forming a dry blend.
  • Milling media e.g. milling beads may, be added to the dry blend to facilitate the mixing process and/or to at least partially embed the electrically conductive particulate into the surface of the polymer particulate.
  • the dry blend may then be coated, using conventional techniques, including but not limited to knife coating and electrostatic coating, on the flow plate substrate.
  • the coating which fills at least one of the at least one flow channel and the at least one via, if present, may then be heat treated at temperatures near, at or above the softening temperature of the polymer particulate, e.g.
  • the glass transition temperature and/or the melting temperature of the polymer particulate to fuse at least a portion of the polymer particulate/carbon particulate dry blend into a porous material, thereby forming a porous electrode material and/or the electrically conductive material.
  • Excess coating may be removed by conventional techniques. In some embodiments, the excess coating is removed prior to heat treatment.
  • the porous electrode material and/or the electrically conductive material may be in the form of a sheet.
  • the thermal treatment may also aid in adhering the electrically conductive carbon particulate to the surface of the polymer particulate.
  • the thermal treatment may be conducted under pressure, e.g. in a heated press or between heated rolls.
  • the press and or heated rolls may be set to provide a specific desired gap, which will facilitate obtaining a desired thickness.
  • the dry blend or the individual particulates may be added to an appropriate liquid medium, i.e. a solvent, and mixed, using conventional techniques, e.g. blade mixing or other agitation, forming a polymer particulate/electrically conductive particulate dispersion.
  • Milling media e.g. milling beads, may be added to the dispersion to facilitate the mixing process and/or to at least partially embed the electrically conductive particulate into the surface of the polymer particulate. If milling media is employed, agitation is usually achieved by shaking or rolling the container holding the dry blend.
  • the dispersion may be coated on the flow plate substrate using conventional techniques, e.g. knife coating, which fills at least one of the at least one flow channel and the at least one via with dispersion.
  • the coating may then be dried, via heat treatment at elevated temperatures, to remove the liquid medium and to fuse at least a portion of the polymer particulate/electrically conductive particulate blend into a porous material, thereby forming a porous electrode material and/or the electrically conductive material.
  • Excess coating may be removed by conventional techniques. In some embodiments, the excess coating is removed prior to heat treatment.
  • the porous electrode material and/or the electrically conductive material may be in the form of a sheet.
  • the thermal treatment may also aid in adhering the electrically conductive particulate to the surface of the polymer particulate.
  • the heat treatment used to dry the dispersion, i.e. evaporate the liquid medium, and to fuse at least a portion of the polymer particulate may be at the same or different temperatures. Vacuum may be used to remove the liquid medium or aid in the removal of the liquid medium.
  • the polymer particulate may be obtained as a dispersion, e.g. the dispersion resulting from a suspension or emulsion polymerization, and the electrically conductive carbon particulate may be added to this dispersion. Mixing, coating, drying and fusing may be conducted as described above.
  • the dry blend or the individual particulates may be added to an appropriate liquid medium, i.e. polymer precursor liquid, and mixed, using conventional techniques, e.g. blade mixing or other agitation, forming a polymer particulate/electrically conductive particulate dispersion.
  • Milling media e.g. milling beads, may be added to the dispersion to facilitate the mixing process and/or to at least partially embed the electrically conductive particulate into the surface of the polymer particulate. If milling media is employed, agitation is usually achieved by shaking or rolling the container holding the dispersion.
  • the dispersion may be coated on the flow plate substrate using conventional techniques, e.g.
  • the coating may then be at least one of dried, cured, polymerized and fused, forming a binder resin and transforming the polymer particulate/electrically conductive particulate blend into a porous material or non-porous material, thereby forming a porous electrode material and/or the electrically conductive material. Excess coating may be removed by conventional techniques. In some
  • the excess coating is removed prior to the at least one of drying, curing, polymerizing and fusing.
  • the porous electrode material and/or the electrically conductive material may be in the form of a sheet. If thermal treatment is used to form the polymer binder resin or a secondary thermal treatment is applied to the polymer binder resin, the temperature may be such that the temperature is near, at or above the softening temperature of the polymer binder resin, e.g. the glass transition temperature and/or the melting temperature of the polymer binder resin, which may aid in the adhering of electrically conductive particulate to the binder resin and/or further fuse the binder resin.
  • an electrically conductive particulate may be dispersed in a polymer precursor liquid and mixed using conventional techniques, e.g. blade mixing or other agitation,.
  • Milling media e.g. milling beads
  • agitation is usually achieved by shaking or rolling the container holding the dispersion.
  • the resulting dispersion may be coated on a flow plate substrate, using conventional techniques, e.g. knife coating, which fills the at least one via with dispersion.
  • the polymer precursor liquid coating may then be at least one of dried, cured, polymerized and fused, forming an electrically conductive polymer composite suitable as an electrically conductive material, e.g. a non-porous electrically conductive material. Excess coating may be removed by conventional techniques. In some
  • the excess coating is removed prior to the at least one of drying, curing, polymerizing and fusing.
  • the electrically conductive material may be in the form of a sheet. If a thermal treatment is used to form the polymer binder resin or a secondary thermal treatment is applied to the polymer binder resin, the temperature may be such that the temperature is near, at or above the softening temperature of the polymer binder resin, e.g. the glass transition temperature and/or the melting temperature of the polymer binder resin, which may aid in the adhering of electrically conductive particulate to the binder resin and/or further fuse the binder resin.
  • the polymer precursor liquid is a polymer solution, e.g. at least one polymer dissolved in at least one solvent, and the electrically, conductive particulate is dispersed in the polymer solution.
  • Milling media e.g. milling beads, may be added to the dispersion to facilitate the mixing process.
  • the resulting dispersion may be coated on a flow plate substrate using conventional techniques, e.g. knife coating, which fills at least one of the at least one flow channel and the at least one via with dispersion.
  • the dispersion coating may be dried, forming a polymer binder resin and a corresponding, porous material, the porous electrode material and/or the electrically conductive material. Excess coating may be removed by conventional techniques.
  • the excess coating is removed prior to drying.
  • the porous electrode material and/or the electrically conductive material may be in the form of a sheet.
  • the temperature may be such that the temperature is near, at or above the softening temperature of the polymer binder resin, e.g. the glass transition temperature and/or the melting temperature of the polymer binder resin, which may aid in the adhering of electrically conductive particulate to the binder resin and/or further fuse the binder resin.
  • the solvent used in the polymer solution is not particularly limited, except that the polymer that will form the polymer binder resin must be soluble in it.
  • the solvent may be selected based on the chemical structure of the polymer and the solubility of the polymer in the solvent.
  • the optional solvent used in the reactive polymer precursor liquid is not particularly limited, except that the at least one of a liquid monomer and a liquid oligomer is soluble in the solvent.
  • Useful solvents include, but are not limited to, water, alcohols (e.g. methanol, ethanol and propanol), acetone, ethyl acetate, alkyl solvents (e.g.
  • the polymer precursor liquid is a reactive polymer precursor liquid, e.g. at least one of a liquid monomer and a liquid oligomer, and the electrically conductive particulate is dispersed in the reactive polymer precursor solution.
  • the reactive polymer precursor may optionally include at least one solvent and may optionally include at least one polymer that is soluble in the liquid components of the reactive polymer precursor liquid.
  • Milling media e.g. milling beads, may be added to the dispersion to facilitate the mixing process.
  • the resulting dispersion may be coated on a flow plate substrate, using conventional techniques, e.g. knife coating, which fills at least one of the at least one flow channel and the at least one via with dispersion.
  • the reactive polymer precursor liquid coating may then be at least one of dried, cured, polymerized and fused, forming a polymer binder resin and a corresponding porous electrode material and/or the electrically conductive material. Excess coating may be removed by conventional techniques. In some
  • the excess coating is removed prior to drying, curing, polymerizing and fusing.
  • the porous electrode material and/or the electrically conductive material may be in the form of a sheet. If a thermal treatment is used to form the polymer binder resin or a secondary thermal treatment is applied to the polymer binder resin, the temperature may be such that the temperature is near, at or above the softening temperature of the polymer binder resin, e.g. the glass transition temperature and/or the melting temperature of the polymer binder resin, which may aid in the adhering of electrically conductive particulate to the binder resin and/or further fuse the binder resin.
  • the reactive polymer precursor liquid may include appropriate additives to aid in the curing and/or polymerization of the reactive polymer precursor liquid.
  • Additives include, but are not limited to catalysts, initiators, curatives, inhibitors, chain transfer agents and the like. Curing and/or polymerization may be conducted by at least one of thermal and radiation. Radiation may include actinic radiation, including UV and visible radiation.
  • the reactive polymer precursor liquid may form a B-stage polymer binder resin, i.e. capable of a second step cure.
  • the first cure may be a thermal cure
  • the second cure may be a radiation cure
  • both curing steps may be thermal cure, for example, at two different cure temperatures
  • both cures may be radiation cure, at two different wavelengths
  • the first cure may be a radiation cure and the second cure a thermal cure.
  • the electrically conductive layer can include any electrically conductive species known in the art.
  • the electrically conductive layer may be a single layer or multiple layers.
  • the electrically conductive layer may include at least one of a metal, e.g. metal film, electrically conductive particulate (e.g. electrically conductive carbon particulate), electrically conductive polymer and electrically conductive polymer composite, as previously described.
  • the electrically conductive layer may include at least one of a metal film, an electrically conductive particulate and an electrically conductive polymer composite comprising polymer and the electrically conductive particulate.
  • the metal may include at least one of silver, copper, gold, aluminum, magnesium, molybdenum, iridium, tungsten, zinc, lead, cobalt, nickel, manganese, ruthenium, lithium, iron, tin, platinum, palladium, tantalum, chromium, antimony, vanadium, titanium, zirconium, bismuth, indium, gallium, and cerium.
  • the electrically conductive layer may include an electrically conductive adhesive, e.g.
  • the electrically conductive adhesive includes at least one of a metal, electrically conductive carbon and electrically conductive polymer.
  • the electrically conductive layer may be in the form of a sheet, e.g. a continuous sheet.
  • a suitable sheet for an electrically conductive layer is a 0.6 mm thick sheet available under the trade designation SIGRACELL TF6, from SGL Carbon GmbH, Meitingen, Germany.
  • the electrically conductive layer may be a discontinuous layer, including a plurality of discrete regions or islands of electrically conductive material.
  • the discrete regions may align with the at least one via, e.g. a plurality of vias, if present, of the flow plate substrate.
  • the electrically conductive layer is impervious to fluid.
  • an electrically conductive layer, which is impervious to fluid will be used when the electrically conductive material contained in the at least one via of the flow plate substrate is a porous material that is not impervious to fluid or when the flow plate substrate includes at least one flow channel, through the depth of the flow plate substrate and the channel contains porous electrode material.
  • the electrically conductive layer, which is impervious to fluid prevents fluid communication between the first major surface and the second major surface of the flow plate substrate, through the thickness of the flow plate substrate.
  • the electrically conductive layer may be laminated, insert molded or compression molded to or with the flow plate substrate.
  • the monopolar plate-electrode assemblies and the bipolar plate-electrode assemblies of the present disclosure may include an ion permeable membrane, ion exchange membranes being particularly useful.
  • Ion permeable membranes and ion exchange membranes known in the art may be used.
  • Ion permeable membranes, e.g. ion exchange membranes are often referred to as separators and may be prepared from ionic polymers.
  • Ionic polymer useful in ion permeable membranes of the present disclosure include, but is not limited to, ion exchange resin and ionomer resin, as previously described and combinations thereof. Ion exchange resins may be particularly useful.
  • the ionic polymer of the ion permeable membrane may include polymer wherein a wherein a fraction of the repeat units is electrically neutral and a fraction of the repeat units have an ionic functional group.
  • the ionic polymer has a mole fraction of repeat units with ionic functional groups between 0.005 and 1, between 0.01 and 1, between 0.05 and 1, between 0.005 and 0.7, between 0.01 and 0.7, between 0.05 and 0.7, between 0.005 and 0.4, between 0.01 and 0.4 or even between 0.05 and 0.4.
  • the ionic polymer is a cationic resin, i.e. its ionic functional groups are negatively charged and facilitate the transfer of cations, e.g.
  • the ionic polymer is an anionic exchange resin, i.e. its ionic functional groups are positively charged and facilitate the transfer of anions.
  • the ionic functional group of the ionic polymer may include, but is not limited, to carboxylate, sulphonate, sulfonamide, quaternary ammonium, thiuronium, guanidinium, imidazolium and pyridinium groups. Combinations of ionic functional groups may be used in an ionic polymer.
  • Ionic polymer may include conventional thermoplastics and thermosets that have been modified by conventional techniques to include at least one of type of ionic functional group, e.g. anionic and/or cationic.
  • Useful thermoplastic resins that may be modified include, but are not limited to, at least one of polyethylene, e.g. high molecular weight polyethylene, high density polyethylene, ultra-high molecular weight polyethylene, polypropylene, e.g. high molecular weight polypropylene, polystyrene, poly(meth)acrylates, e.g. polyacrylates based on acrylic acid that may have the acid functional group exchanged for, for example, an alkali metal, chlorinated polymer, e.g.
  • thermoset resins include, but are not limited to, at least one of epoxy resin, phenolic resin, polyurethanes, urea-formadehyde resin and melamine resin.
  • the ion permeable membranes may include a fluorinated ion exchange resin.
  • Ion permeable membranes useful in the embodiments of the present disclosure may be fabricated from ion exchange resins and/or ionomer known in in the art or may be commercially available as membrane films and include, but are not limited to, NAFION PFS A MEMBRANES, available from DuPont, Wilmington, Delaware; AQUIVION PFSA, a perfluorosulfonic acid, available from
  • FLEMION and SELEMION fluoropolomer ion exchange membranes, available from Asahi Glass, Tokyo, Japan
  • FUMASEP ion exchange membranes including FKS, FKB, FKL, FKE cation exchange membranes and FAB, FAA, FAP and FAD anionic exchange membranes, available from Fumatek, Bietigheim-Bissingen, Germany and ion exchange membranes, perfluorosulfonic acid ionomer having an 825 equivalent weight, available under the trade designation "3M825EW", available as a powder or aqueous solution, from the 3M Company, St.
  • the ion exchange membrane includes a fluoropolymer.
  • the fluoropolymer of the ion exchange membrane may contain from 10% to 90%, from 20% to 90%, from 30% to 90% or even from 40% to 90% fluorine by weight.
  • the ion permeable membranes of the present disclosure may be obtained as free standing films from commercial suppliers or may be fabricated by coating a solution of the appropriate membrane resin, e.g. ion exchange membrane resin, in an appropriate solvent, and then heating to remove the solvent.
  • the membrane may be formed from a coating solution by coating the solution on a release liner and then drying the membrane coating solution coating to remove the solvent.
  • Any suitable method of coating may be used to coat the membrane coating solution on a release liner.
  • Typical methods include both hand and machine methods, including hand brushing, notch bar coating, fluid bearing die coating, wire-wound rod coating, fluid bearing coating, slot-fed knife coating, and three-roll coating. Most typically three-roll coating is used. Coating may be achieved in one pass or in multiple passes. Coating in multiple passes may be useful to increase coating weight without corresponding increases in cracking of the ion permeable membrane.
  • the amount of solvent, on a weight basis, in the membrane coating solution may be from 5 to 95 percent, from 10 to 95 percent, from 20 to 95 percent, from 30 to 95 percent, from 40 to 95 percent, from 50 to 95 percent, from 60 to 95 percent, from 5 to 90 percent, from 10 to 90 percent, from 20 percent to 90 percent, from 30 to 90 percent, from 40 to 90 percent, from 50 to 90 percent, from 60 to 90 percent, from 5 to 80 percent, from 10 to 80 percent from 20 percent to 80 percent, from 30 to 80 percent, from 40 to 80 percent, from 50 to 80 percent, from 60 to 80 percent, from 5 percent to 70 percent, from 10 percent to 70 percent, from 20 percent to 70 percent, from 30 to 70 percent, from 40 to 70 percent, or even from 50 to 70 percent..
  • the amount of membrane resin, e.g. ion exchange resin and ionomer resin, on a weight basis, in the membrane coating solution may be from 5 to 95 percent, from 5 to 90 percent, from 5 to 80 percent, from 5 to 70 percent, from 5 to 60 percent, from 5 to 50 percent, from 5 to 40 percent, from 10 to 95 percent, from 10 to 90 percent, from 10 to 80 percent, from 10 to 70 percent, from 10 to 60 percent, from 10 to 50 percent, from 10 to 40 percent, from 20 to 95 percent, from 20 to 90 percent, from 20 to 80 percent, from 20 to 70 percent, from 20 to 60 percent, from 20 to 50 percent, from 20 to 40 percent, from 30 to 95 percent, from 30 to 90 percent, from 30 to 80 percent, from 30 to 70 percent, from 30 to 60 percent, or even from 30 to 50 percent.
  • ion exchange resin and ionomer resin on a weight basis
  • the thickness of the ion permeable membrane may be from 5 microns to 250 microns, from 5 microns to 200 microns, from 5 microns to 150 microns, from 5 microns to 100 microns, from 10 microns to 250 microns, from 10 microns to 200 microns, from 10 microns to 150 microns, from 5 microns to 10 microns, from 15 microns to 250 microns, from 15 microns to 200 microns, from 15 microns to 150 microns, or even from 15 microns to 100 microns.
  • the monopolar plate-electrode assemblies and bipolar plate- electrode assemblies of the present disclosure may include a discontinuous transport protection layer.
  • the discontinuous transport protection layer protects the ion permeable membrane from puncture by the electrically conductive particulate, e.g. carbon fibers, of the porous electrode material and thus may prevents localized shorting that has been found to be an issue in some electrochemical cell and liquid flow battery designs.
  • the discontinuous transport protection layers of the present disclosure may also improve fluid flow within the monopolar plate and bipolar plate-electrode assemblies and subsequently fluid flow within an electrochemical cell and/or battery.
  • transport within the phrase “transport protection layer” refers to fluid transport within and/or through the protection layer.
  • discontinuous refers to the porous nature of the transport protection layer, which allows fluid communication through at least its thickness, i.e. between the first major surface and the opposed second major surface of the discontinuous transport protection layer. This may lead to improved, i.e. decreased, or at least not significantly altered cell resistance, contrary to what one might expect to occur with the inclusion of an additional layer within the monopolar and the bipolar plate-electrode assemblies and subsequently with the inclusion of an additional layer in an electrochemical cell and/or battery.
  • the discontinuous transport protection layer is generally a porous layer, e.g. a nonwoven or woven fabric or mesh material, providing a space between the porous electrode material and the ion permeable membrane.
  • the thickness of the discontinuous transport protection layer may be from 25 microns to 3000 microns, from 25 microns to 2000 microns, from 25 microns to 1000 microns, from 25 microns to 500 microns, from 50 microns to 3000 microns, from 50 microns to 2000 microns, from 50 microns to 1000 microns, from 50 microns to 500 microns, from 75 microns to 3000 microns, from 75 microns to 2000 microns, from 75 microns to 1000 microns, from 75 microns to 500 microns, from 100 microns to 3000 microns, from 100 microns to 2000 microns, from 100 microns to 1000 microns, or even from 100 microns to 500 microns.
  • the bipolar plate-electrode assemblies of the present disclosure may be used to fabricate an electrochemical cell stack for use in, for example, a liquid flow battery, e.g. a redox flow battery.
  • an electrochemical cell for a liquid flow battery includes two half cells, each half cell including an electrode (e.g. anode or cathode).
  • the number of electrochemical cells in an electrochemical cell stack is not particularly limited.
  • the present disclosure provides an electrochemical cell stack that includes at least one bipolar plate-electrode assembly of the present disclosure.
  • the present disclosure provides an electrochemical cell stack including a bipolar plate-electrode assembly according to any one of the bipolar plate-electrode assemblies of the present disclosure.
  • the present disclosure provides an electrochemical cell stack including at least one, at least two, at least five, at least ten, at least twenty, at least fifty or even more bipolar plate-electrode assembly/assemblies according to any one of the bipolar plate-electrode assemblies of the present disclosure.
  • the present disclosure provides an electrochemical cell stack for a liquid flow battery comprising two electrochemical cells, each including two half cells and corresponding electrodes, and a bipolar plate-electrode assembly according to any one of the bipolar plate-electrode assemblies of the present disclosure, wherein a half cell from each of the two electrochemical cells includes a monopolar plate-electrode assembly of the bipolar plate-electrode assembly.
  • the electrode of the half cell that includes the first monopolar plate- electrode assembly of the bipolar plate-electrode assembly consists essentially of the first porous electrode material of the first monopolar plate-electrode assembly.
  • the electrode of at least one of the half cells that includes the bipolar plate- electrode assembly consists essentially of a porous electrode material, e.g. a first porous electrode material.
  • each electrode of the two half cells that include the bipolar plate electrode assembly consists essentially of a porous electrode material, e.g. a first porous electrode material and a second porous electrode material, respectively, wherein the first and second porous electrode material for each bipolar plate-electrode assembly may be the same or different (two different porous electrode materials).
  • Individual bipolar plate-electrode assemblies may be arranged to form an
  • the electrochemical cell stacks of the present disclosure may include at least one bipolar plate-electrode assembly, according to the present disclosure.
  • the electrochemical cell stacks of the present disclosure may include a plurality of bipolar plate-electrode assemblies.
  • the present disclosure provides an electrochemical cell stack including at least two, at least three, at least five, at least ten, at least twenty, at least fifty or even more bipolar plate-electrode assemblies, according to any one of the bipolar plate-electrode assemblies of the present disclosure.
  • the bipolar plate-electrode assemblies of the electrochemical cell stack may all have the same construction.
  • one or more of the bipolar plate- electrode assemblies of the electrochemical cell stack may differ from a first bipolar plate- electrode assembly of the electrochemical cell stack.
  • FIG. 8 shows a schematic cross-sectional side view of an exemplary electrochemical cell stack according to one exemplary embodiment of the present disclosure.
  • Electrochemical cell stack 600 includes bipolar plate-electrode assemblies 500-1 and 500-3, as previously described (see FIGS. 7 A and 7C and corresponding text) and two monopolar plate-electrode assemblies 100 and 101, as previously described (see FIGS. 2A though 2D and 4A through 4D and corresponding text), on either end of cell stack 600.
  • Cell stack 600 also includes ion permeable membranes 80, separating the bipolar plate-electrode assemblies from each other and the adjacent monopolar plate-electrode assemblies. Any of the monopolar plate-electrode assemblies of the present disclosure may be used for the monopolar plate-electrode assemblies shown in FIG. 8, including ones that include a conventional flow plate and a conventional electrode.
  • the two bipolar plate-electrode assemblies combine with the two monopolar plate electrode assemblies to form three electrochemical cells, SI, S2 and S3.
  • Electrochemical cells SI and S2 include bipolar plate electrode assembly 500-1.
  • Electrochemical cells S2 and S3 include bipolar plate electrode assembly 500-3. Each cell is configured into two half cells, an anode half cell (al, a2 and a3 in FIG. 8) and a cathode half cell (cl, c2 and c3 in FIG. 8).
  • the right half cells of the two bipolar plate electrode assemblies, a2 and a3, and the monopolar plate- electrode assembly on the left of the cell stack which represents half cell al are configured, via appropriate plumbing as known in the art, to allow anolyte to flow through one set of flow channels of the bipolar plate electrode assemblies and the flow channels of the left monopolar plate electrode assembly.
  • the left half cells of the two bipolar plate electrode assemblies, cl and c2, and the monopolar plate-electrode assembly on the right of the cell stack which represents half cell c3, are configured, via appropriate plumbing as known in the art, to allow catholyte to flow through one set of flow channels of the bipolar plate electrode assemblies and the flow channels of the right monopolar plate electrode assembly.
  • Electrochemical cell stack 600 also may include current collectors 201 and 202. If one or more of the monopolar plate-electrode assemblies or bipolar plate-electrode assemblies of an individual cell include an integral ion permeable membrane (see FIG. 6C-1 and FIG. 7E, for example), the corresponding, separate ion permeable membrane 80 shown in FIG. 8 may not be required. Within an electrochemical cell stack, the bipolar plate-electrode assemblies may be the same or may be different.
  • electrically conductive layer 70 may be an electrically conductive adhesive layer, the electrically conductive adhesive layer bonding a first monopolar plate-electrode assembly to a second monopolar plate-electrode assembly, thereby forming a bipolar plate-electrode assembly.
  • Support plates may be placed adjacent to the exterior surfaces of current collectors 201 and 202. The support plates are electrically isolated from the current collector and provide mechanical strength and support to facilitate compression of the cell assembly.
  • the anolyte and catholyte inlet and outlet ports and corresponding fluid distribution system are not shown. These features may be provided as known in the art.
  • the bipolar plate-electrode assemblies and their corresponding electrochemical cells and cell stacks of the present disclosure may be used to fabricate liquid flow batteries, e.g. a redox flow battery.
  • the number of electrochemical cells in a liquid flow battery is not particularly limited.
  • the present disclosure provides a liquid flow battery that includes at least one bipolar plate-electrode assembly according to the present disclosure.
  • the present disclosure provides a liquid flow battery that includes at least two, at least three, at least five, at least ten, at least twenty, at least fifty or even more bipolar plate-electrode assemblies, according to any one of the bipolar plate- electrode assemblies of the present disclosure.
  • the bipolar plate- electrode assemblies of the liquid flow battery may all have the same construction. In some embodiments, one or more bipolar plate-electrode assemblies of the liquid flow battery may differ from a first bipolar plate-electrode assembly of the liquid flow battery. In one embodiment, the present disclosure provides a liquid flow battery including a bipolar plate- electrode assembly according to any one of the bipolar plate-electrode assemblies of the present disclosure, for example bipolar plate-electrode assemblies 500-1 through 500-8.
  • the present disclosure provides a liquid flow battery comprising two electrochemical cells, each including two half cells and corresponding electrodes, and a bipolar plate-electrode assembly according to any one of the bipolar plate-electrode assemblies of the present disclosure, wherein a half cell from each of the two electrochemical cells includes a monopolar plate-electrode assembly of the bipolar plate-electrode assembly.
  • the electrode of the half cell that includes the first monopolar plate- electrode assembly of the bipolar plate-electrode assembly consists essentially of the first porous electrode material of the first monopolar plate-electrode assembly.
  • the electrode of at least one of the half cells that includes the bipolar plate- electrode assembly consists essentially of the porous electrode material, e.g. the first porous electrode material.
  • each electrode of the two half cells that include the bipolar plate electrode assembly consists essentially of the porous electrode material, e.g. the first porous electrode material and a second porous electrode material, respectively, wherein the first and second porous electrode material for each bipolar plate-electrode assembly may be the same or different (two different porous electrode materials).
  • FIG. 9 shows a schematic view of an exemplary two cell, liquid flow battery according to one exemplary embodiment of the present disclosure.
  • Liquid flow battery 700 includes bipolar plate-electrode assembly 500-2 previously described (see FIG. 7B and corresponding text) and two monopolar plate-electrode assemblies 100, as previously described (see FIGS. 2A though 2D and corresponding text), on either end of the cell stack.
  • Liquid flow battery 700 also includes ion permeable membranes 80, separating the bipolar plate-electrode assembly from the adjacent monopolar plate-electrode assemblies. Any of the monopolar plate-electrode assemblies of the present disclosure may be used for the monopolar plate-electrode assemblies shown in FIG. 9, including ones that include a conventional flow plate and a conventional electrode.
  • Liquid flow battery 700 may also include current collectors 201 and 202, anolyte reservoir 220 and anolyte fluid distribution 220', and catholyte reservoir 222 and catholyte fluid distribution system 222'. Pumps for the fluid distribution system are not shown.
  • Current collectors 201 and 202 may be connected to an external circuit which includes an electrical load (not shown).
  • Support plates not shown, may be placed adjacent to the exterior surfaces of current collectors 201 and 202. The support plates are electrically isolated from the current collector and provide mechanical strength and support to facilitate compression of the cell assembly. Flow fields may be present, but this is not a requirement.
  • multiple cell stacks may be used to form a liquid flow battery. The multiple cell stacks may be connected in series.
  • the bipolar plate-electrode assemblies of the present disclosure may provide improved cell short resistance and cell resistance.
  • Cell short resistance is a measure of the resistance an electrochemical cell has to shorting, for example, due to puncture of the membrane by conductive fibers of the electrode.
  • a test cell, as described in the Example section of the present disclosure, which includes at least one of a an electrode assembly and membrane-electrode assembly of the present disclosure may have a cell short resistance of greater than 1000 ohm-cm 2 , greater than 5000 ohm-cm 2 or even greater than 10000 ohm-cm 2 . In some embodiments, the cell short resistance may be less than 10000000 ohm-cm 2 .
  • a test cell as described in the Example section of the present disclosure, which includes at least one bipolar plate-electrode assembly of the present disclosure may have a cell resistance of between 0.01 and 10 ohm-cm 2 , 0.01 and 5 ohm-cm 2 , between 0.01 and 3 ohm-cm 2 , between 0.01 and 1 ohm-cm 2 , between 0.04 and 5 ohm-cm 2 , between 0.04 and 3 ohm-cm 2 , between 0.04 and 0.5 ohm-cm 2 , between 0.07 and 5 ohm-cm 2 , between 0.07 and 3 ohm-cm 2 or even between 0.07 and 0.1 ohm-cm 2 .
  • the liquid flow battery may be a redox flow battery, for example, a vanadium redox flow battery (VRFB), wherein a V J 7 V 2+ sulfate solution serves as the negative electrolyte ("anolyte”) and a V 5 V 4 ⁇ sulfate solution serves as the positive electrolyte (“catholyte”).
  • VRFB vanadium redox flow battery
  • anolyte negative electrolyte
  • catholyte positive electrolyte
  • other redox chemistries are contemplated and within the scope of the present disclosure, including, but not limited to, V 2 7V 3';” vs. BrVClBn, Bn/Br " vs. S/S 2 ⁇ BrTBnvs.
  • the components of the cell, cell stack and liquid flow battery may be configured one adjacent to the other in the desired sequence; e.g.
  • a first monopolar plate-electrode assembly an ion permeable membrane, a second monopolar plate-electrode assembly, a third monopolar plate electrode assembly, wherein the second major surface of the flow plate substrate of the second monopolar plate- electrode assembly is adjacent to the second major surface of the flow plate substrate of the third monopolar plate-electrode assembly (forming a bipolar plate-electrode assembly), a second ion permeable membrane and a second monopolar plate-electrode assembly; and then held together by mechanical means, for example, by an electrochemical cell frame, an electrochemical cell stack frame or liquid flow battery frame, as is known in the art. In this manner, a bipolar plate may be formed without the aid of electrically conductive layer.
  • bipolar plate electrode assemblies may also be formed from a first and a second monopolar plate-electrode assembly using an electrically conductive layer.
  • the electrically conductive layer adheres the second major surface of the flow plate substrate of the first monopolar plate-electrode assembly to the second major surface of the flow plate substrate of the second monopolar plate electrode assembly, forming a bipolar plate-electrode assembly, i.e. an integral bipolar plate-electrode assembly.
  • each individual cell, each individual cell of a cell stack and each individual cell of a liquid flow battery may be electrically isolated in the non-electrochemically active areas of the cell, as is known in the art.
  • the perimeter region of a given cell may be electrically isolated from any other given cell.
  • the electrochemical cells, electrochemical cell stacks and liquid flow batteries of the present disclosure may be actively cooled. Cooling/heating cells in the stack may be provided, or the reactants may be temperature controlled remotely such as inline heat exchangers or temperature control in the reactant tanks may be provided.
  • the present disclosure also provides methods of making a monopolar plate-electrode assembly.
  • the method of making an monopolar plate-electrode assembly includes (i) providing a flow plate substrate having a first major surface and an opposed second major surface in the x-y plane of the monopolar plate electrode assembly, wherein the first major surface includes at least one flow channel, allowing fluid flow in the x-y plane of the monopolar plate electrode assembly, wherein the depth of the at least one flow channel extends through the thickness of the flow plate substrate and wherein the at least one flow channel is in fluid communication with a fluid inlet port and a fluid outlet port of the flow plate substrate, (ii) disposing a porous electrode material in at least a portion of the at least one flow channel (iii) disposing an electrically conductive layer onto the second major surface of the flow plate substrate, wherein the electrically conductive layer is impervious to fluid and wherein the electrically conductive layer is in electrical
  • a method of making an monopolar plate-electrode assembly includes (i) providing a flow plate substrate having a first major surface and an opposed second major surface in the x-y plane of the monopolar plate-electrode assembly, wherein the first major surface includes at least one flow channel, allowing fluid flow in the x-y plane of the monopolar plate-electrode assembly, the at least one flow channel is in fluid
  • the flow plate substrate includes at least one via intersecting the channel bottom of the at least one flow channel and the second major surface of the flow plate substrate, (ii) disposing a porous electrode material in at least a portion of the at least one flow channel (iii) disposing an electrically conductive material in at least a portion of the at least one via, wherein the electrically conductive material is in electrical communication with the porous electrode material, thereby forming monopolar plate-electrode assembly wherein the monopolar plate-electrode assembly exhibits electrical communication through the thickness of the flow plate substrate and does not exhibit fluid communication through the thickness of the flow plate substrate.
  • the method may further include disposing an electrically conductive layer adjacent to and in contact with the second major surface of the flow plate substrate, wherein the electrically conductive layer is impervious to fluid.
  • the step of disposing a porous electrode material in at least a portion of the at least one flow channel and the step of disposing an electrically conductive material in at least a portion of the at least one via are conducted in a single step.
  • the disposing step or steps may include providing at least one of pressure and heat to at least one of the porous electrode material and/or electrically conductive material.
  • the disposing step includes at least one of coating, e.g. knife coating a polymer, polymer composite or polymer precursor (the polymer precursor may contain electrically conductive particulate); extruding, e.g. melt extruding a polymer, polymer composite or polymer precursor; and printing, e.g. 3-dimensional printing and ink jet printing a polymer, polymer composite or polymer precursor.
  • coating, e.g. knife coating, and extrusion processes, e.g. polymer melt extrusion, and polymer printing are well known in the art and conventional techniques may be employed in the fabrication of the monopolar plate- electrode assemblies of the present disclosure.
  • the present disclosure provides a method of making a bipolar plate-electrode assembly including providing (i) a first flow plate substrate having a first major surface and an opposed second major surface in the x-y plane of the first monopolar plate electrode assembly, wherein the first major surface includes at least one first flow channel, allowing fluid flow in the x-y plane of the first monopolar plate electrode assembly, wherein the depth of the at least one first flow channel extends through the thickness of the first flow plate substrate and wherein the at least one first flow channel is in fluid communication with a first fluid inlet port and a first fluid outlet port of the first flow plate substrate, (ii) a first porous electrode material contained in at least a portion of the at least one first flow channel, and (iii) a first electrically conductive layer in contact with the second major surface of the first flow plate substrate, wherein the first electrically conductive layer is impervious to fluid and the electrically conductive layer is an electrically conductive adhesive layer; (B) providing a second monopolar plate-electrode assembly
  • the present disclosure provides a bipolar plate-electrode assembly including:
  • a first monopolar plate-electrode assembly comprising:
  • a first flow plate substrate having a first major surface and an opposed second major surface in the x-y plane of the first monopolar plate electrode assembly, wherein the first major surface includes at least one first flow channel, allowing fluid flow in the x-y plane of the first monopolar plate electrode assembly, wherein the depth of the at least one first flow channel extends through the thickness of the first flow plate substrate and wherein the at least one first flow channel is in fluid communication with a first fluid inlet port and a first fluid outlet port of the first flow plate substrate;
  • first electrically conductive layer in contact with the second major surface of the first flow plate substrate, wherein the first electrically conductive layer is impervious to fluid
  • a second monopolar plate-electrode assembly comprising:
  • a second flow plate substrate having a first major surface and an opposed second major surface in the x-y plane of the bipolar plate-electrode assembly, wherein the first major surface includes at least one second flow channel, allowing fluid flow in the x-y plane of the second monopolar plate-electrode assembly, the at least one second flow channel is in fluid communication with a second fluid inlet port and a second fluid outlet port of the second flow plate substrate, and wherein the second major surface of the second flow plate substrate is adjacent to the second major surface of the first electrically conductive layer, and wherein the bipolar plate-electrode assembly exhibits electrical communication through the thickness of the flow plate substrates and does not exhibit fluid communication through the thickness of the flow plate substrates.
  • the present disclosure provides a bipolar plate-electrode assembly according to the first embodiment, wherein the second flow plate substrate includes at least one via intersecting the channel bottom of the at least one second flow channel and the second major surface of the second flow plate substrate and wherein the second flow plate substrate further includes a second porous electrode material contained in at least a portion of the at least one second flow channel and a second electrically conductive material contained in at least a portion of the at least one via of the second flow plate substrate, wherein the second electrically conductive material is in electrical communication with the second porous electrode material.
  • the present disclosure provides a bipolar plate-electrode assembly according to the second embodiment, wherein the at least one via of the second flow plate substrate is a plurality of vias.
  • the present disclosure provides a bipolar plate-electrode assembly according to the second embodiment, wherein the at least one via of the second flow plate substrate is a single via.
  • the present disclosure provides a bipolar plate-electrode assembly according to the first embodiment, wherein the depth of the at least one second flow channel extends through the thickness of the second flow plate substrate and the second flow plate substrate further comprises a second porous electrode material contained in at least a portion of the at least one second flow channel.
  • the present disclosure provides a bipolar plate-electrode assembly according to the fifth embodiment, further comprising a second electrically conductive layer in contact with the second major surface of the second flow plate substrate, wherein the second electrically conductive layer is impervious to fluid, and the second flow plate substrate does not exhibit fluid communication between the first major surface and the second major surface, through the thickness of the second flow plate substrate.
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the first through sixth embodiments, wherein at least one of the first flow plate substrate and second flow plate substrate is an electrically conductive flow plate substrate.
  • the present disclosure provides a bipolar plate-electrode assembly according to the seventh embodiment, wherein the electrically conductive flow plate substrate includes at least one of a metal, electrically conductive carbon, electrically conductive polymer and electrically conductive polymer composite.
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the first through sixth embodiments, wherein at least one of the first flow plate substrate and second flow plate substrate is a dielectric flow plate substrate.
  • the present disclosure provides a bipolar plate-electrode assembly according to the ninth embodiment, wherein the dielectric flow plate substrate includes at least one dielectric polymer.
  • the present disclosure provides a bipolar plate-electrode assembly according to the tenth embodiment, wherein the at least one dielectric polymer includes at least one of epoxy resin, phenolic resin, ionic polymer, polyurethane, urea- formadehyde resin, melamine resin, polyesters, polyamide, polyether, polycarbonate, polyimide, polysulphone, polyphenylene oxide, polyacrylates, polymethacrylates, polyolefin, styrene and styrene based random and block copolymers, , polyvinyl chloride, and fluorinated polymer.
  • the at least one dielectric polymer includes at least one of epoxy resin, phenolic resin, ionic polymer, polyurethane, urea- formadehyde resin, melamine resin, polyesters, polyamide, polyether, polycarbonate, polyimide, polysulphone, polyphenylene oxide, polyacrylates, polymethacrylates, polyolefin, st
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the first through eleventh embodiments, wherein the first porous electrode material includes electrically conductive carbon particulate.
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the fifth through twelfth embodiments, wherein at least one of the first porous electrode material and second porous electrode material includes electrically conductive carbon particulate.
  • the present disclosure provides a bipolar plate-electrode assembly according to the twelfth or thirteenth embodiments, wherein the electrically conductive carbon particulate is at least one of carbon particles, carbon flakes, carbon fibers, carbon dendrites, carbon nanotubes and branched carbon nanotubes.
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the first through fourteenth embodiments, wherein the first electrically conductive material includes at least one of a metal film and an electrically conductive polymer composite comprising polymer and electrically conductive particulate.
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the sixth through fifteenth embodiments, wherein at least one of the first electrically conductive material and second electrically conductive material includes at least one of a metal material and an electrically conductive polymer composite comprising polymer and electrically conductive particulate.
  • the present disclosure provides a bipolar plate-electrode assembly according to the sixteenth embodiment, wherein the metal material includes at least one of silver, copper, gold, aluminum, magnesium, molybdenum, iridium, tungsten, zinc, lead, cobalt, nickel, manganese, ruthenium, lithium, iron, tin, platinum, palladium, tantalum, chromium, antimony, vanadium, titanium, zirconium, bismuth, indium, gallium, and cerium.
  • the metal material includes at least one of silver, copper, gold, aluminum, magnesium, molybdenum, iridium, tungsten, zinc, lead, cobalt, nickel, manganese, ruthenium, lithium, iron, tin, platinum, palladium, tantalum, chromium, antimony, vanadium, titanium, zirconium, bismuth, indium, gallium, and cerium.
  • the present disclosure provides a bipolar plate-electrode assembly according to the sixteenth or seventeenth embodiments, wherein the polymer of the electrically conductive polymer composite includes at least one of polyalkylenes,
  • polyacrylates polymethacrylates, styrene and styrene based random and block copolymers, polyesters, polycarbonates, polyamides, polyamide-amines, polyalkylene glycols, polyurethanes, polyethers, polyvinyl chloride; fluoropolymers, polyimides, polyetherimides, polysulphones; polyphenylene oxides; and polyketones, epoxy resin, phenolic resin, urea- formadehyde resin and melamine resin.
  • the present disclosure provides a bipolar plate-electrode assembly according to the fifteenth, sixteenth or eighteenth embodiments, wherein the electrically conductive particulate of the electrically conductive polymer composite includes at least one of metal particulate, electrically conductive carbon particulate and electrically conductive polymer particulate.
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the first through nineteenth embodiments, wherein the first electrically conductive material is impervious to fluid.
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the sixth through twentieth embodiments, wherein at least one of the first electrically conductive material and second electrically conductive material is impervious to fluid.
  • the present disclosure provides a bipolar plate- electrode assembly according to any one of the first through twenty-first embodiments, wherein the flow first plate substrate has a thickness from 0.025 cm to 3.2 cm.
  • the present disclosure provides a bipolar plate- electrode assembly according to any one of the second through twenty -first embodiments, wherein at least one of the first flow plate substrate and second flow plate substrate has a thickness from 0.025 cm to 3.2 cm.
  • the present disclosure provides a bipolar plate- electrode assembly according to any one of the first through twenty -third embodiments further comprising a first ion permeable membrane disposed adjacent the first major surface of the first flow plate substrate.
  • the present disclosure provides a bipolar plate- electrode assembly according to any one of the first through twenty -third embodiments further comprising at least one of a first ion permeable membrane disposed adjacent the first major surface of the first flow plate substrate and a second ion permeable membrane disposed adjacent the first major surface of the second flow plate substrate.
  • the present disclosure provides a bipolar plate- electrode assembly according to the twenty-fourth embodiment further comprising a first discontinuous transport protection layer disposed between the first ion permeable membrane and the first major surface of the first flow plate substrate.
  • the present disclosure provides a bipolar plate- electrode assembly according to the twenty-fifth embodiment further comprising at least one of a first discontinuous transport protection layer disposed between the first ion permeable membrane and the first major surface of the first flow plate substrate and a second discontinuous transport protection layer disposed between the second ion permeable membrane and the first major surface of the second flow plate substrate.
  • the present disclosure provides a bipolar plate- electrode assembly according to any one of the first through twenty-seventh embodiments, wherein the first electrically conductive layer adheres the second major surface of the first flow plate substrate to the second major surface of the second flow plate substrate.
  • the present disclosure provides a bipolar plate- electrode assembly according to any one of the first through twenty-eighth embodiments, wherein the first electrically conductive layer is at least one of an electrically conductive pressure sensitive adhesive, an electrically conductive hot melt adhesive and an electrically conductive thermosetting adhesive.
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the sixth through twenty -ninth embodiments, wherein the second electrically conductive layer is at least one of an electrically conductive pressure sensitive adhesive, an electrically conductive hot melt adhesive and an electrically conductive thermosetting adhesive.
  • the present disclosure provides a bipolar plate-electrode assembly according to the first embodiment further comprising a porous electrode material adjacent the first major surface of the second flow plate substrate, optionally, wherein the porous electrode material comprises at least one of a carbon fiber woven and non-woven substrate.
  • the present disclosure provides an electrochemical cell stack for a liquid flow battery including at least one bipolar plate-electrode assembly according to any one of the first through thirty-first embodiments.
  • the present disclosure provides an electrochemical cell stack for a liquid flow battery comprising two electrochemical cells, each including two half cells and corresponding electrodes, and a bipolar plate-electrode assembly according to any one of the first through thirty -first embodiments, wherein a half cell from each of the two electrochemical cells includes a monopolar plate-electrode assembly of the bipolar plate- electrode assembly.
  • the present disclosure provides an electrochemical cell stack for a liquid flow battery according to the thirty -third embodiment, wherein the electrode of at least one of the half cells that includes a monopolar plate-electrode assembly consists essentially of the porous electrode material.
  • the present disclosure provides a liquid flow battery including at least one bipolar plate-electrode assembly according to any one of the first through thirty -first embodiments.
  • liquid flow battery comprising two electrochemical cells, each including two half cells and corresponding electrodes, and a bipolar plate-electrode assembly according to any one of the first through thirty-first embodiments, wherein a half cell from each of the two electrochemical cells includes a monopolar plate-electrode assembly of the bipolar plate-electrode assembly.
  • the present disclosure provides liquid flow battery according to the thirty-sixth embodiment, wherein the electrode of at least one of the half cells that includes a monopolar plate-electrode assembly consists essentially of the porous electrode material.
  • a bipolar plate-electrode assembly was placed on a metal plate. Using a Tektronix
  • An electrode solution was prepared as follows. Water, 60 ml, was poured into a 500 ml beaker with a teflon coated magnetic stir bar. One drop of Palmolive Original dish soap was added. (Colgate-Palmolive Company, New York). The beaker was placed on a magnetic stir plate and the plate was turned on to a medium setting. TREVIRA 255, 0.2 gm, was added to the beaker and allowed to mix for a minimum of 30 sec to disperse the fibers into the water. ANS, 0.8 gm, was broken up using mortar and pestle, added to solution and allowed to mix for a minimum of 30 sec. Granco XN-100-05M, 1.0 gm, was added to mixture and allowed to mix for a minimum of 30 sec, producing Electrode Solution 1.
  • POLYPROPYLENE NATURAL from Plastics International, Eden Prairie, MN, having dimensions of 0.78 mm thick x 300 mm x 280 mm or two sheet of polyvinylchloride available under the trade designation PVC TYPE 1, from Plastics International, Eden Prairie, MN having dimensions of 1.57 mm thick x 300 mm x 280 mm were stacked together and placed on the metal tooling that contained the inverse dimensions of four flow fields, enabling the formation of four flow plate substrates in a single step (once separated via cutting of the polypropylene or the PVC).
  • the flow field pattern of the metal tooling was machined into a plastic substrate that was subsequently metal plated using known techniques.
  • the resultant flow fields of each of the four flow plate substrates had the following dimensions after pressing.
  • Manifold Depth 0.75 mm The length of the manifold is parallel to the channel array width allowing the manifold to be in fluid communication with all of the channels. Vias, having a diameter of 0.43 mm and extending though the thickness of the flow plate substrate, were machined. All the vias were located within a channel and the center-to-center distance, between adjacent vias within a channel, was 2.95 mm.
  • POLYPROPYLENE NATURAL from Plastics International, Eden Prairie, MN, having dimensions of 0.78 mm thick x 300 mm x 280 mm were stacked together and placed on the metal tooling that contained the inverse dimensions of four flow fields, enabling the formation of four flow plate substrates in a single step (once separated via cutting of the polypropylene).
  • the flow field pattern of the metal tooling was machined into a plastic substrate that was subsequently metal plated using known techniques.
  • the metal tooling with polypropylene sheets adjacent the flow field pattern were pressed in a compression molder, Rucker PHI 400 ton (City of Industry, CA). The molding conditions used are noted below. Note the "Cure" step is essentially a water cooling step.
  • the resultant flow fields of each of the four flow plate substrates had the following dimensions after pressing.
  • Manifold Depth 0.75 mm The length of the manifold is parallel to the channel array width allowing the manifold to be in fluid communication with all of the channels. Vias, having a diameter of 0.43 mm and extending though the thickness of the flow plate substrate, were machined. All the vias were located within a channel and the center-to-center distance, between adjacent vias within a channel, was 2.95 mm.
  • the molded flow plate substrate was modified by milling out a 45 mm x 45 mm square, in the land region of the flow plate substrate directly under the channels, leaving only the ribs between the channels.
  • the resultant flow plate substrate had a pocket to place a conductive layer.
  • the coating apparatus consisted of a clear, plastic tube having a 101 mm inside diameter and a length of 100 mm long; a flow plate substrate holder which was composed of two equal half-cylinders that, when placed adjacent to each other to form a cylinder, had an outside diameter of 101 mm, a length of 63.6 mm and had a 53.2 mm x 62 mm rectangular hole that extended through the length of the cylinder; a plastic frame having a diameter of 101 mm, a thickness of 6.3 mm, a rectangular recess, 1 mm in depth x 71 mm x 63 mm, machined in the middle of the frame and, in the center of the recess, a rectangular hole, 62 mm x 53.2 mm, in which the length and width aligned with the length and width of recess.
  • the plastic frame has four through holes along the perimeter of the rectangular recess, two each adjacent the 63 mm width of the recess.
  • the bottom of each half cylinder of the flow plate substrate holder has two threaded holes that aligned with the through holes of the plastic frame. This enables the half cylinders to be attached to the plastic frame by a set of four screws and, once assembled, also allows the flow plate substrate to be securely held between the plastic frame and flow plate substrate holder.
  • Flow Plate Substrate 1 was cut into a rectangle, 71 mm x 63 mm, with the flow field channels centered within the rectangle.
  • the flow plate substrate was placed in the recess of the plastic frame of the coating apparatus with the flow fields oriented upwards.
  • the two half cylinders of the flow plate substrate holder were placed on top of the flow plate substrate and attached to the plastic frame via four screws, forming an assembly.
  • the clear plastic tube was placed in a Buchner funnel having an inside diameter of 101 mm.
  • the Buchner funnel is mounted to a 2000 ml vacuum flask.
  • the assembly was then placed inside the clear plastic tube with the plastic frame oriented adjacent the Buchner funnel bottom.
  • Electrode Solution 1 was then poured into the rectangular hole of the flow plate substrate holder.
  • Flow Plate Substrate 2 was cut into a rectangle, 71 mm x 63 mm, with the flow field channels centered within the rectangle.
  • a conductive layer was 45 mm x 45 mm machined sheets of SIGRACELL BIPOLAR PLATE TF6 available from SGL Carbon, GmbH, Meitingen, Germany. The machined sheets were placed in the pocket of the flow plate substrate such that they formed the bottom of the channels and extended to the back side of the molded flow plate substrate, thus providing a portion of the conductive path through the thickness of the flow plate substrate.
  • the flow plate substrate was placed in the recess of the plastic frame of the coating apparatus with the flow fields oriented upwards.
  • the two half cylinders of the flow plate substrate holder were placed on top of the flow plate substrate and attached to the plastic frame via four screws, forming an assembly.
  • the clear plastic tube was placed in a Buchner funnel having an inside diameter of 101 mm.
  • the Buchner funnel is mounted to a 2000 ml vacuum flask.
  • the assembly was then placed inside the clear plastic tube with the plastic frame oriented adjacent the Buchner funnel bottom.
  • Electrode Solution 1 was then poured into the rectangular hole of the flow plate substrate holder.
  • a 101 mm diameter x 12.9 mm thick disk was then placed on top of the clear tube and the vacuum was turned on. Excess fluid drained from the sample around the flow plate substrate holder and into the Buchner funnel.
  • Monopolar Plate-Electrode Assembly 1 having vias, was bonded to Monopolar Plate- Electrode Assembly 2, having a conductive layer, to form a bipolar plate-electrode assembly.
  • the monopolar plate-electrode assemblies were positioned next to one another, such that, the major surfaces of each assembly that did not have flow channels were adjacent to and in contact with each other.
  • the monopolar plate-electrode assemblies were bonded together by using polyimide tape, available under the trade designation 5413 (1 "X36YDS) Polyimide Film Tape from 3M Company, St Paul MN. The tape was first dispensed onto a table top (backing side down) and then cut into 0.5 inch (1.4 cm) strips using a razor.
  • Example 1 a bipolar plate-electrode assembly

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Abstract

La présente invention concerne des ensembles plaques-électrodes bipolaires et des empilements de cellules électrochimiques et des batteries à flux liquide produites à partir de ceux-ci. Les ensembles plaques-électrodes bipolaires comprennent au moins un ensemble plaque-électrode monopolaire qui comprend (i) un substrat de plaque d'écoulement ayant une première surface principale et une seconde surface principale opposée, la première surface principale comprenant au moins un canal d'écoulement et la profondeur de l'au moins un premier canal d'écoulement s'étendant à travers l'épaisseur du premier substrat de plaque d'écoulement; (ii) un matériau d'électrode poreux contenu dans au moins une partie de l'au moins un canal d'écoulement; et (iii) une première couche électroconductrice en contact avec la seconde surface principale du premier substrat de plaque d'écoulement, la première couche électroconductrice étant imperméable au fluide. L'invention concerne en outre des procédés de fabrication des ensembles plaques-électrodes bipolaires.
PCT/US2017/065964 2016-12-13 2017-12-13 Ensembles plaques-électrodes bipolaires et empilements de cellules électrochimiques et batteries à flux liquide produites à partir de ceux-ci WO2018111968A1 (fr)

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DE102019207702A1 (de) * 2019-05-27 2020-12-03 Robert Bosch Gmbh Bipolarplatte
EP3761420A1 (fr) * 2019-07-01 2021-01-06 Commissariat à l'énergie atomique et aux énergies alternatives Dispositif de diffusion gazeuse pour réduire les pertes de charge
CN113733548A (zh) * 2021-08-05 2021-12-03 西安交通大学 一种面向曲面ipmc的4d打印方法
CN114051664A (zh) * 2019-07-01 2022-02-15 原子能和替代能源委员会 用于制造具有改善的电气特性的气体扩散设备的方法
WO2022263174A1 (fr) * 2021-06-14 2022-12-22 Robert Bosch Gmbh Empilement de piles à combustible et système de pile à combustible

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US20120077095A1 (en) * 2010-09-09 2012-03-29 Roumi Farshid Electrochemical Energy Storage Systems and Methods
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US3617387A (en) * 1969-02-20 1971-11-02 Union Carbide Corp Battery construction having cell components completely internally bonded with adhesive
US20040151975A1 (en) * 1999-11-16 2004-08-05 Allen Jeffrey P. Fuel cell bipolar separator plate and current collector assembly and method of manufacture
US20060057286A1 (en) * 2004-09-13 2006-03-16 Gibbons Daniel W Method of applying adhesive to electrochemical cell components
US20120077095A1 (en) * 2010-09-09 2012-03-29 Roumi Farshid Electrochemical Energy Storage Systems and Methods
US20140072836A1 (en) * 2011-04-05 2014-03-13 Blacklight Power, Inc. H2o-based electrochemical hydrogen-catalyst power system
WO2016154194A1 (fr) * 2015-03-24 2016-09-29 3M Innovative Properties Company Électrodes poreuses, ainsi que cellules électrochimiques et batteries à écoulement de liquide produites à partir de celles-ci

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019207702A1 (de) * 2019-05-27 2020-12-03 Robert Bosch Gmbh Bipolarplatte
EP3761420A1 (fr) * 2019-07-01 2021-01-06 Commissariat à l'énergie atomique et aux énergies alternatives Dispositif de diffusion gazeuse pour réduire les pertes de charge
FR3098356A1 (fr) * 2019-07-01 2021-01-08 Commissariat à l'Energie Atomique et aux Energies Alternatives Dispositif de diffusion gazeuse pour réduire les pertes de charge
CN114051664A (zh) * 2019-07-01 2022-02-15 原子能和替代能源委员会 用于制造具有改善的电气特性的气体扩散设备的方法
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WO2022263174A1 (fr) * 2021-06-14 2022-12-22 Robert Bosch Gmbh Empilement de piles à combustible et système de pile à combustible
CN113733548A (zh) * 2021-08-05 2021-12-03 西安交通大学 一种面向曲面ipmc的4d打印方法

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