WO2018111962A1 - Ensembles d'électrodes à plaque bipolaires et empilements de cellules électrochimiques et batteries à écoulement liquide à partir de ces derniers - Google Patents

Ensembles d'électrodes à plaque bipolaires et empilements de cellules électrochimiques et batteries à écoulement liquide à partir de ces derniers Download PDF

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Publication number
WO2018111962A1
WO2018111962A1 PCT/US2017/065957 US2017065957W WO2018111962A1 WO 2018111962 A1 WO2018111962 A1 WO 2018111962A1 US 2017065957 W US2017065957 W US 2017065957W WO 2018111962 A1 WO2018111962 A1 WO 2018111962A1
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Prior art keywords
electrically conductive
flow
bipolar plate
electrode assembly
polymer
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PCT/US2017/065957
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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 WO2018111962A1 publication Critical patent/WO2018111962A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
    • H01M8/0252—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form tubular
    • 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
    • H01M8/0232—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
    • H01M8/023—Porous and characterised by the material
    • H01M8/0239—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
    • H01M8/023—Porous and characterised by the material
    • H01M8/0241—Composites
    • 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
    • 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
    • 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 including (i) a 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 includes at least one first flow channel, allowing fluid flow in the x-y plane of the bipolar plate electrode assembly, 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 flow plate substrate; and the second major surface includes at least one second flow channel, allowing fluid flow in the x-y plane of the bipolar plate electrode assembly, wherein 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 flow plate substrate; and an electrically conductive region disposed between the at least one first flow channel and the at least one second flow channel and intersecting the channel bottom of the at least one first flow channel and the channel bottom of the at least one second flow channel; (ii) a first porous electrode material contained in at least
  • the electrically conductive region comprises at least one of an electrically conductive material having the same composition as that of the flow plate substrate, wherein the electrically conductive material is in electrical communication with the first and second porous electrode materials; and at least one via in the flow plate substrate and an electrically conductive material contained in at least a portion of the at least one via, wherein the electrically conductive material is in electrical communication with the first and second porous electrode materials
  • the present disclosure provides a method of making a bipolar plate-electrode assembly including (i) providing a 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 includes at least one first flow channel, allowing fluid flow in the x-y plane of the bipolar plate electrode assembly, 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 flow plate substrate; and the second major surface includes at least one second flow channel, allowing fluid flow in the x-y plane of the bipolar plate electrode assembly, wherein 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 flow plate substrate; and an electrically conductive region disposed between the at least one first flow channel and the at least one second flow channel and intersecting the channel bottom of the at least one first flow channel and the channel bottom of the at least one second flow channel, (ii) disposing
  • 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 each includes a portion 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 each includes a portion of the bipolar plate-electrode assembly.
  • FIG. 1A 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 flow plate substrate according to one exemplary embodiment of the present disclosure.
  • FIG. 2B is a schematic bottom view of the exemplary flow plate substrate of FIG. 2A according to one exemplary embodiment of the present disclosure.
  • FIG. 2C is a schematic cross-sectional side view of the exemplary flow plate substrate 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 flow plate substrate of FIG. 2A 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 bipolar plate-electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 4B is a schematic bottom view of the exemplary bipolar 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 bipolar 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 bipolar plate-electrode assembly of FIG. 4 A according to one exemplary embodiment of the present disclosure.
  • FIG. 5 A is a schematic top view of an exemplary bipolar plate-electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 5B is a schematic bottom view of the exemplary bipolar plate-electrode assembly 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 bipolar plate- electrode assembly 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 bipolar plate-electrode assembly of FIG. 5 A according to one exemplary embodiment of the present disclosure.
  • FIG. 6A is a schematic top view of an exemplary bipolar plate-electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 6B is a schematic bottom view of the exemplary bipolar 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 bipolar 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 bipolar plate-electrode assembly of FIG. 6 A according to one exemplary embodiment of the present disclosure.
  • FIG. 7A is a schematic cross-sectional side view of an exemplary bipolar plate- electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 7B is a schematic cross-sectional side view of an exemplary bipolar plate- electrode assembly according to one exemplary embodiment of the present disclosure.
  • FIG. 7C is a schematic cross-sectional side view of an 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.
  • a substrate or a surface of a substrate is "adjacent" to a second substrate or a surface of a second substrate, the two nearest surfaces of the two substrates are considered to be facing one another. They may be in contact with one another or they may not be in contact with one another, an intervening third layer(s) or substrate(s) being disposed between them.
  • non-conductive refers to a material or substrate that is non-electrically conductive, unless otherwise stated.
  • 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.
  • a bipolar flow plate is 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 bipolar anode and cathode flow plate may be fabricated by a variety of techniques including machining (e.g. milling), molding (e.g.
  • the present disclosure provides bipolar plate-electrode assemblies.
  • the bipolar plate- electrode assemblies combine a bipolar flow plate substrate (e.g. having a cathode and anode portion) with at least one porous electrode material contained in at least a portion of the at least one flow channels of the bipolar flow plate substrate.
  • a bipolar flow plate substrate e.g. having a cathode and anode portion
  • at least one porous electrode material contained in at least a portion of the at least one flow channels of the bipolar flow plate substrate.
  • at least 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 bottom of the flow channels of the bipolar 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 communication with the porous electrode material contained in the flow channels.
  • the bipolar 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 the electrically conductive material within the at least one via, i.e. the bipolar plate-electrode assemblies exhibit electrical communication through the thickness of the flow plate substrate.
  • a single flow plate substrate having a first major surface and an opposed second major surface, each surface including at least one flow channel (a first and a second flow channel, respectively) is fabricated and a porous electrode material is disposed in at least a portion of each of the at least one flow channel.
  • the flow plate substrate includes an electrically conductive region disposed between the at least one first flow channel and the at least one second flow channel and intersects the channel bottom of the at least one first flow channel and the channel bottom of the at least one second flow channel.
  • the electrically conductive region disposed between the at the flow channels includes an electrically conductive material having the same composition as that of the flow plate substrate.
  • the electrically conductive region disposed between the flow channels includes at least one via in the flow plate substrate and an electrically conductive material is contained in at least a portion of the at least one via, wherein the electrically conductive material is in electrical communication with the porous electrode materials contained in the flow channels.
  • the electrically conductive region may be impervious to fluid. This produces a bipolar plate-electrode assembly having electrical communication through the thickness of the flow plate substrate but does not have fluid communication through the thickness of the flow plate substrate.
  • 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 or it may be fabricated from an easily processed and inexpensive composite material e.g. an electrically conductive polymer composite.
  • the flow plate substrate may be fabricated from electrically conductive materials, e.g. metal.
  • the flow plate substrate, porous electrode material and electrically conductive material (if used) of a bipolar-plate electrode assembly, which may form an integral structure, will be referred to as a bipolar plate-electrode assembly.
  • the bipolar plate- electrode assembly may be used in an electrochemical cell, electrochemical cell stack and/or liquid flow battery.
  • the bipolar plate-electrode assembly may further include a first ion permeable membrane adjacent to a major surface of the bipolar flow plate substrate. In some embodiments, the bipolar plate-electrode assembly may further include a second ion permeable membrane adjacent to the other major surface of the bipolar flow plate substrate.
  • the bipolar plate-electrode assembly may further include a first discontinuous transport protection layer adjacent to a major surface of the bipolar flow plate substrate. In some embodiments, the bipolar plate-electrode assembly may further include a second discontinuous transport protection layer adjacent to the other major surface of bipolar flow plate substrate.
  • 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 (i) a 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 includes at least one first flow channel, allowing fluid flow in the x-y plane of the bipolar plate electrode assembly, 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 flow plate substrate; and the second major surface includes at least one second flow channel, allowing fluid flow in the x-y plane of the bipolar plate electrode assembly, wherein 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 flow plate substrate; and an electrically conductive region disposed between the at least one first flow channel and the at least one second flow channel and intersecting the channel bottom of the at least one first flow channel and the channel bottom of the at least one second flow channel; (ii) a first porous electrode material contained in at least a
  • the electrically conductive region includes at least one of (i) an electrically conductive material having the same composition as that of the flow plate substrate, wherein the electrically conductive material is in electrical communication with the first and second porous electrode materials; and (ii) at least one via in the flow plate substrate and an electrically conductive material contained in at least a portion of the at least one via, wherein the electrically conductive material is in electrical communication with the first and second porous electrode materials.
  • the flow plate substrate is an electrically conductive flow plate substrate.
  • the flow plate substrate is a dielectric flow plate substrate; and the electrically conductive region comprises at least one via in the flow plate substrate and an electrically conductive material contained in at least a portion of the at least one via, wherein the electrically conductive material is in electrical communication with the first and second porous electrode materials.
  • the at least one via of the flow plate substrate may be a single via or a plurality of vias.
  • the electrically conductive material is impervious to fluid.
  • the electrically conductive material may include at least one of at least one of a metal, electrically conductive carbon, electrically conductive polymer and electrically conductive polymer composite.
  • the electrically conductive material may include at least one of an electrically conductive sheet, e.g. a metal sheet; an electrically conductive pin, e.g. a metal pin; and a plurality of electrically conductive pins, e.g. a plurality of metal pins.
  • the porous electrode material (e.g. first and/or second porous electrode material) and the electrically conductive material may include electrically conductive particulate, e.g.
  • the porous electrode material and 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.
  • At least one of the distal surface of the first major surface and the second major surface of the flow plate substrate may be free of porous electrode material and/or a conventional electrode, e.g. carbon fiber mat.
  • 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.
  • 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.
  • the layer of porous electrode material may be considered to be part of the major surface of the flow plate substrate.
  • 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 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 flow plate substrate and a second ion permeable membrane disposed adjacent the second major surface of the flow plate substrate.
  • the first ion permeable membrane may be in contact with the first major surface of the flow plate substrate and/or the second ion permeable membrane may be in contact with the second major surface of the 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 flow plate substrate and/or an optional, second discontinuous transport protection layer disposed adjacent the second major surface of the 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 flow plate substrate and a second discontinuous transport protection layer disposed adjacent the second major surface of the flow plate substrate.
  • discontinuous transport protection layer may be in contact with the first major surface of the flow plate substrate and/or the second discontinuous transport protection layer may be in contact with the second major surface of the flow plate substrate.
  • Embodiments that contain an ion permeable membrane may further include at least one of a first discontinuous transport protection layer disposed between the first ion permeable membrane and the first major surface of the flow plate substrate and a second discontinuous transport protection layer disposed between the second ion permeable membrane and the second major surface of the flow plate substrate.
  • FIGS. 1 A through ID, FIGS. 2A through 2D and FIGS. 3 A through 3D show various, non-limiting, embodiments of flow plate substrates suitable for bipolar plate-electrode assemblies of the present disclosure and FIGS. 4A through 4D, FIGS. 5A through 5D and FIGS. 6A through 6D show the corresponding exemplary bipolar plate-electrode assemblies utilizing the flow plate substrates of FIGS. 1 A through ID, FIGS. 2A through 2D and FIGS. 3 A through 3D, respectively.
  • the flow plate substrates 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).
  • First major surface 10a includes at least one first 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).
  • Second major surface 10b includes at least one second flow channel 22 with a bottom 22b (see FIG.
  • FIG. IB shows a schematic bottom view of the exemplary flow plate substrate 10 of FIG. 1 A and includes second major surface 10b and the at least one second flow channel 22.
  • FIG. 1C shows a schematic cross-sectional side view of the exemplary flow plate substrate 10 of FIG. 1A through line 1C.
  • FIG. ID is a schematic side view of the front face of the exemplary flow plate substrate 10 of FIG. 1 A.
  • Flow plate substrate 10 of FIG. ID shows front face lOff and includes first major surface 10a and second major surface 10b and first and second inlet ports 30a and 32a, respectively, of front face lOff.
  • Flow plate substrate 10 has thickness, T.
  • FIG. 2A is a schematic top view and FIG. 2B 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. 2B).
  • First major surface 11a includes at least one first flow channel 20 with a bottom 20b (see FIG. 2C) 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).
  • Second major surface 1 lb includes at least one second flow channel 22 with a bottom 22b (see FIG.
  • FIG. 2C shows a schematic cross-sectional side view of the exemplary flow plate substrate 11 of FIG. 2A through line 2C.
  • Flow plate substrate 11 of FIG. 2C includes first major surface 11a and second major surface 1 lb, at least one first flow channel 20 having channel bottom 20b and a depth, Da, a width, Wa and at least one second flow channel 22 having channel bottom 22b and a depth, Db, a width, Wb.
  • Flow plate substrate 11 includes an electrically conductive region 25 disposed between at least one first flow channel 20 and at least one second flow channel 22 and intersecting the channel bottom 20b of the at least one first flow channel 20 and the channel bottom 22b of the at least one second flow channel 22.
  • Electrically conductive region 25 includes at least one via 40 in flow plate substrate 11.
  • the at least one via has a height, H.
  • the at least one via is a single via.
  • the single via may span the entire width and length (x-y dimensions) of the at least one first flow channel 20 and/or the at least one second flow channel 22.
  • FIG. 2D is a schematic side view of the front face of the exemplary flow plate substrate 11 of FIG. 2A.
  • Flow plate substrate 11 of FIG. 2D shows front face 1 Iff and includes first major surface 11a and second major surface 1 lb and first inlet port 30a and second inlet port 32a of front face 1 Iff Flow plate substrate 11 has thickness, T.
  • FIG. 3 A is a schematic top view and FIG. 3B 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. 3B).
  • First major surface 12a includes at least one first 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).
  • Second major surface 12b includes at least one second flow channel 22 with a bottom 22b (see FIG.
  • FIG. 3C shows a schematic cross-sectional side view of the exemplary flow plate substrate 12 of FIG. 3A through line 3C.
  • Flow plate substrate 12 of FIG. 3C includes first major surface 12a and second major surface 12b, at least one first flow channel 20 having channel bottom 20b and a depth, Da, a width, Wa and at least one second flow channel 22 having channel bottom 22b and a depth, Db, a width, Wb.
  • Flow plate substrate 12 includes an electrically conductive region 25 disposed between at least one first flow channel 20 and at least one second flow channel 22 and intersecting the channel bottom 20b of the at least one first flow channel 20 and the channel bottom 22b of the at least one second flow channel 22.
  • Electrically conductive region 25 includes at least one via 40 in flow plate substrate 12.
  • the at least one via has a height, H.
  • the at least one via is a plurality of vias. The plurality of vias may be dispersed across the entire width and length (x-y dimensions) of the at least one first flow channel 20 and/or the at least one second flow channel 22.
  • FIG. 3D is a schematic side view of the front face of the exemplary flow plate substrate 12 of FIG. 3A.
  • Flow plate substrate 12 of FIG. 3D shows front face 12ff and includes first major surface 12a and second major surface 12b and first inlet port 30a and second inlet port 32a of front face 12ff
  • Flow plate substrate 12 has thickness, T.
  • FIGS. 4A through 4D are schematic views of exemplary bipolar plate-electrode assembly 500 which includes flow plate substrate 10 of FIGS. 1 A through ID, 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. 4 A
  • FIG. 4D is a schematic side view of the front face of the exemplary bipolar plate-electrode assembly 500.
  • Bipolar plate-electrode assembly 500 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 bipolar plate.
  • First major surface 10a includes at least one flow channel 20, allowing fluid flow in the x-y plane of the bipolar plate
  • second major surface 10b includes at least one flow channel 22, allowing fluid flow in the x-y plane of the bipolar plate.
  • bipolar plate-electrode assembly 500 includes first porous electrode material 50 contained in at least a portion of the at least one first flow channel 20 and second porous electrode material 52 contained in at least a portion of the at least one second flow channel 22.
  • the first porous electrode material and second porous electrode material may be the same porous electrode material or may be different porous electrode materials.
  • Bipolar plate-electrode assembly 500 includes electrically conductive region 25 of flow plate substrate 10.
  • electrically conductive region 25 includes electrically conductive material 40 having the same composition as that of the flow plate substrate 10.
  • the electrically conductive material is in electrical communication with the first and second porous electrode materials.
  • the electrically conductive region is impervious to fluid.
  • Bipolar plate-electrode assembly 500 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. 4D shows a schematic side view of the front face 500ff of the bipolar plate-electrode assembly 500 of FIG. 4A.
  • FIGS. 5A through 5D are schematic views of exemplary bipolar plate-electrode assembly 501 which includes flow plate substrate 11 of FIGS. 2A through 2D, according to one exemplary embodiment of the present disclosure.
  • FIG. 5A is a schematic top view
  • FIG. 5B is a schematic bottom view
  • FIG. 5C is a schematic cross-sectional side view, though line 5C of FIG. 5 A
  • FIG. 5D is a schematic side view of the front face of the exemplary bipolar plate-electrode assembly 501.
  • Bipolar plate-electrode assembly 501 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 bipolar plate.
  • First major surface 11a includes at least one flow channel 20, allowing fluid flow in the x-y plane of the bipolar plate
  • second major surface 1 lb includes at least one flow channel 22, allowing fluid flow in the x-y plane of the bipolar plate.
  • bipolar plate-electrode assembly 501 includes first porous electrode material 50 contained in at least a portion of the at least one first flow channel 20 and second porous electrode material 52 contained in at least a portion of the at least one second flow channel 22.
  • the first porous electrode material and second porous electrode material may be the same porous electrode material or may be different porous electrode materials.
  • Bipolar plate-electrode assembly 501 includes electrically conductive region 25 of flow plate substrate 11.
  • electrically conductive region 25 includes at least one via 40 in flow plate substrate 11.
  • the at least one via is a single via.
  • Electrically conductive material 60 is contained in at least a portion of the at least one via. Electrically conductive material 60 is in electrical communication with first porous electrode material 50 and second porous electrode material 52. The electrically conductive region is impervious to fluid.
  • Bipolar plate-electrode assembly 501 exhibits electrical communication between first major surface 11a and second major surface 1 lb, through the thickness of the flow plate substrate (z-axis), 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 (z-axis).
  • FIG. 5D shows a schematic side view of the front face 501ff of the bipolar plate-electrode assembly 500 of FIG. 5A.
  • FIGS. 6A through 6D are schematic views of exemplary bipolar plate-electrode assembly 502 which includes flow plate substrate 12 of FIGS. 3A through 3D, 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. 6 A
  • FIG. 6D is a schematic side view of the front face of the exemplary bipolar plate-electrode assembly 502.
  • Bipolar plate-electrode assembly 502 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 bipolar plate.
  • First major surface 12a includes at least one flow channel 20, allowing fluid flow in the x-y plane of the bipolar plate, and second major surface 12b includes at least one flow channel 22, allowing fluid flow in the x-y plane of the bipolar plate.
  • bipolar plate-electrode assembly 502 includes first porous electrode material 50 contained in at least a portion of the at least one first flow channel 20 and second porous electrode material 52 contained in at least a portion of the at least one second flow channel 22.
  • the first porous electrode material and second porous electrode material may be the same porous electrode material or may be different porous electrode materials.
  • Bipolar plate-electrode assembly 502 includes electrically conductive region 25 of flow plate substrate 12.
  • electrically conductive region 25 includes at least one via 40 in flow plate substrate 12.
  • the at least one via is plurality of vias.
  • Electrically conductive material 60 is contained in at least a portion of the at least one via, e.g. is contained in a portion of the plurality of vias. Electrically conductive material 60 is in electrical communication with first porous electrode material 50 and second porous electrode material 52. The electrically conductive region is impervious to fluid.
  • Bipolar plate-electrode assembly 502 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).
  • FIG. 6D shows a schematic side view of the front face 502ff of the bipolar plate-electrode assembly 502 of FIG. 6A.
  • the porous electrode material combined with the electrically conductive material in electrical communication therewith enable the bipolar-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.
  • the fluid impervious electrically conductive material may allow the electrically conductive region to be fluid impervious and may inhibit 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 bipolar plate electrode assemblies of the present disclosure may further include a first ion permeable membrane disposed adjacent the first major surface of the flow plate substrate and a second ion permeable membrane disposed adjacent the second major surface of the 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 flow plate substrate.
  • bipolar plate electrode assemblies of the present disclosure may include a second ion permeable membrane disposed adjacent the second major surface of the 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 flow plate substrate and a second ion permeable membrane disposed adjacent to and in contact with the second major surface of the flow plate substrate.
  • FIG. 7 A is a schematic cross-sectional side view of an exemplary bipolar plate- electrode assembly 500-1, similar to bipolar plate-electrode assembly 500 of FIG. 4C, except bipolar plate-electrode assembly 500-1 further includes a first ion permeable membrane 80a adjacent to first major surface 10a of flow plate substrate 10.
  • ion permeable membrane 80a is adjacent to and in contact with first major surface 10a of flow plate substrate 10.
  • bipolar plate-electrode assembly 500-1 may further include a second ion permeable membrane 80b adjacent to second major surface 10b of flow plate substrate 10.
  • FIG. 7 A is a schematic cross-sectional side view of an exemplary bipolar plate- electrode assembly 500-1, similar to bipolar plate-electrode assembly 500 of FIG. 4C, except bipolar plate-electrode assembly 500-1 further includes a first ion permeable membrane 80a adjacent to first major surface 10a of flow plate substrate 10.
  • ion permeable membrane 80a is adjacent to and in contact with
  • second ion permeable membrane 80b is adjacent to and in contact with first major surface 10b of flow plate substrate 10.
  • Any of the bipolar plate-electrode assemblies of the present disclosure e.g. bipolar plate-electrode assemblies 501, 502 and 503, may include a first ion permeable membrane adjacent to the first major surface of the flow plate substrate and/or an ion permeable membrane adjacent to the second major surface of the flow plate substrate.
  • 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 flow plate substrate and a second discontinuous transport protection layer disposed adjacent the second major surface of the 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 flow plate substrate. In some embodiments, bipolar plate electrode assemblies of the present disclosure may include a second discontinuous transport protection layer disposed adjacent the second major surface of the flow plate substrate. In some embodiments, 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 flow plate substrate and a second discontinuous transport protection layer disposed adjacent to and in contact with the second major surface of the 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 flow plate substrate and/or a second discontinuous transport protection layer disposed between the second ion permeable membrane and the second major surface of the fl ow pi ate sub strate .
  • FIG. 7B is a schematic cross-sectional side view of an exemplary bipolar plate- electrode assembly 501-1, similar to bipolar plate-electrode assembly 501 of FIG. 5C, except bipolar plate-electrode assembly 501-1 further includes a first discontinuous transport protection layer 90a adjacent to first major surface 1 la of flow plate substrate 11.
  • first discontinuous transport protection layer 90a is adjacent to and in contact with first major surface 1 la of flow plate substrate 11.
  • bipolar plate-electrode assembly 501-1 may further include a second discontinuous transport protection layer 90b adjacent to second major surface 1 lb of flow plate substrate 11.
  • FIG. 7B is a schematic cross-sectional side view of an exemplary bipolar plate- electrode assembly 501-1, similar to bipolar plate-electrode assembly 501 of FIG. 5C, except bipolar plate-electrode assembly 501-1 further includes a first discontinuous transport protection layer 90a adjacent to first major surface 1 la of flow plate substrate 11.
  • first discontinuous transport protection layer 90a is adjacent to and in contact
  • second discontinuous transport protection layer 90b is adjacent to and in contact with first major surface 1 lb of flow plate substrate 10.
  • Any of the bipolar plate-electrode assemblies of the present disclosure e.g. bipolar plate-electrode assemblies 501, 502 and 503, may include a first discontinuous transport protection adjacent to the first major surface of the flow plate substrate and/or a second discontinuous transport protection adjacent to the second major surface of the flow plate substrate.
  • FIG. 7C is a schematic cross-sectional side view of an exemplary bipolar plate- electrode assembly 502-1, similar to bipolar plate-electrode assembly 502 of FIG. 6C, except bipolar plate-electrode assembly 502-1 further includes a first discontinuous transport protection layer 90a adjacent to first major surface 12a of flow plate substrate 12.
  • first discontinuous transport protection layer 90a is adjacent to and in contact with first major surface 12a of flow plate substrate 12.
  • bipolar plate-electrode assembly 502-1 may further include a second discontinuous transport protection layer 90b adjacent to second major surface 12b of flow plate substrate 12.
  • FIG. 7C is a schematic cross-sectional side view of an exemplary bipolar plate- electrode assembly 502-1, similar to bipolar plate-electrode assembly 502 of FIG. 6C, except bipolar plate-electrode assembly 502-1 further includes a first discontinuous transport protection layer 90a adjacent to first major surface 12a of flow plate substrate 12.
  • first discontinuous transport protection layer 90a is adjacent to and in contact with first major surface 12a of
  • second discontinuous transport protection layer 90b is adjacent to and in contact with first major surface 12b of flow plate substrate 12.
  • bipolar plate-electrode assembly 502-1 further includes an optional, first ion permeable membrane 80a disposed adjacent the first discontinuous transport protection layer 90a and an optional, second ion permeable membrane 80b disposed adjacent to the second discontinuous transport protection layer 90b.
  • first ion permeable membrane 80a is disposed adjacent to and in contact with first discontinuous transport protection layer 90a and second ion permeable membrane 80b is disposed adjacent to and in contact with second
  • any of the bipolar plate-electrode assemblies of the present disclosure may include a first discontinuous transport protection adjacent to the first major surface of the flow plate substrate and/or a second discontinuous transport protection adjacent to the second major surface of the flow plate substrate along with an optional first ion permeable membrane adjacent the first discontinuous transport protection layer and an optional second ion permeable membrane adjacent the second discontinuous transport protection layer.
  • Any of the bipolar plate-electrode assemblies of the present disclosure e.g.
  • bipolar plate-electrode assemblies 501, 502 and 503 may include a first discontinuous transport protection adjacent to the first major surface of the flow plate substrate and/or a second discontinuous transport protection adjacent to the second major surface of the flow plate substrate along with an optional first ion permeable membrane adjacent to and in contact with the first discontinuous transport protection layer and an optional second ion permeable membrane adjacent to and in contact with the second discontinuous transport protection layer.
  • an ion permeable membrane may be adhered to the first major surface of the flow plate substrate of the bipolar plate-electrode assembly, the ion permeable membrane thereby being integral to and part of the bipolar 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.
  • the flow plate substrate of the present disclosure is a not a combination of two monopolar flow plate substrates that have been laminated together to form a bipolar flow plate substrate, i.e. the flow plate substrate of the present disclosure may be considered a unitary flow plate substrate.
  • the phrase "flow plate substrate” and the phrase “unitary flow plate substrate” may be used interchangeably.
  • 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.
  • the flow plate substrate, along with the at least one first flow channel, the at least one second flow channel and/or the at least one via 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 substrate of the desired thickness followed by one or more machining steps to form at least one of or both of the flow channels 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 flow channels and the at least one via 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.
  • Conventional molding techniques include pressing; embossing; molding, e.g. injection molding, insert molding and compression molding; 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. For example, if insert injection molding of a polymer or polymer composite is used to form the flow plate substrate, a plurality of electrically conductive pins, e.g.
  • 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 at least one first flow channel and the at least one second flow channel are not particularly limited, except by the dimension of the flow plate substrate, as the at least one first flow channel and the at least one second flow channel must be capable of being contained within the dimensions of the flow plate substrate.
  • the depth, D, of the at least one first flow channel and the at least one second 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 widths, Wa and Wb, of the at least one first flow channel and the at least one second flow channel, respectively 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 widths, Wa and Wb, of the at least one first flow channel and the at least one second flow channel, respectively 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 first flow channel and the at least one second flow channel may each be a serpentine flow channel or may each 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 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, 1 A-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 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 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 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 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.
  • 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 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 e.g. first porous electrode material and second 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 e.g. the first porous electrode material and the second porous electrode material, may be a combination of porous electrode materials.
  • 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 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
  • 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 (below).
  • 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.
  • 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
  • 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.
  • 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, 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
  • 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.
  • 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.
  • 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 embodiments, 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 optional 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, 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.
  • 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 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 are 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 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 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 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 each includes a portion of the bipolar plate-electrode assembly.
  • the electrode of one of the half cell that includes a portion of the bipolar plate-electrode assembly consists essentially of the first porous electrode material of the bipolar plate- electrode assembly.
  • the electrode of at least one of the half cells that includes a portion of the bipolar plate-electrode assembly consists essentially of a porous electrode material, e.g. the first porous electrode material or the second 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. the first porous electrode material and the second porous electrode material, respectively.
  • the first and second porous electrode material for a 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 501 and 502, as previously described (see FIGS. 5C and 6C and corresponding text) and two conventional monopolar plates 15 and two conventional electrodes 55 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 conventional electrodes 55.
  • the two bipolar plate-electrode assemblies combine with the two monopolar plates and the two conventional electrodes to form three electrochemical cells, SI, S2 and S3.
  • Electrochemical cells SI and S2 include bipolar plate electrode assembly 501.
  • Electrochemical cells S2 and S3 include bipolar plate electrode assembly 502. 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 and conventional electrode 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.
  • Electrochemical cell stack 600 also may include current collectors 201 and 202. If one or more of the bipolar plate-electrode assemblies of an individual cell include an integral ion permeable membrane (see FIG. 7 A, for example), the corresponding, separate ion permeable membrane 80 shown in FIG. 8 may not be required.
  • the bipolar plate-electrode assemblies may be the same or may be different.
  • 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 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.
  • 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, e.g. differ in composition between the first and second porous electrode materials.
  • 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, 500-1, 501, 501-1, 502 and 502-1.
  • 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 each includes a portion of the bipolar plate-electrode assembly.
  • the electrode of the half cell that includes the portion of the bipolar plate-electrode assembly consists essentially of the porous electrode material, e.g. the first porous electrode material, of the bipolar 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 a portion of 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.
  • the first and second porous electrode material of a 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 502 previously described (see FIG. 6C and corresponding text) and two conventional monopolar plates 15 and two conventional electrodes 55 on either end of cell stack of the liquid flow battery.
  • Liquid flow battery 700 also includes ion permeable membranes 80, separating the bipolar plate-electrode assembly from the adjacent conventional electrodes 55.
  • Any of the bipolar plate-electrode assemblies of the present disclosure may be used for the monopolar plate-electrode assemblies shown in FIG. 9, e.g. bipolar plate-electrode assemblies 500, 500-1, 501, 501-1, 502 and 502-1.
  • 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 .
  • Cell resistance is a measure of the electrical resistance of 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
  • 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 batter ⁇ ', for example, a vanadium redox flow battery (VRFB), wherein a V 3 7 V 2 ⁇ sulfate solution serves as the negative electrolyte ("anolyte”) and a V 5 7V 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, ⁇ / ⁇ vs. S/S 2"" , BrTBn vs.
  • components of the cell, cell stack and liquid flow batten' may be configured one adjacent to the other in the desired sequence; e.g. a first conventional monopolar plate, a first conventional electrode, a first ion permeable membrane, a bipolar plate-electrode assembly, a second ion permeable membrane, a second conventional electrode and a second conventional monopolar plate; 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.
  • each individual ceil 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 ceil.
  • 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.
  • a method of making an bipolar 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 bipolar plate-electrode assembly; the first major surface includes at least one first flow channel, allowing fluid flow in the x-y plane of the bipolar plate electrode assembly, 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 flow plate substrate; and the second major surface includes at least one second flow channel, allowing fluid flow in the x-y plane of the bipolar plate electrode assembly, wherein 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 flow plate substrate; and an electrically conductive region disposed between the at least one first flow channel and the at least one second flow channel and intersecting the channel bottom of the at least one first flow channel and the channel bottom of the
  • the disposing step or steps may include providing at least one of pressure and heat to at least one of the first and second porous electrode material. Providing at least one of pressure and heat to at least one of the first and second porous electrode material may urge the porous electrode material into the at least one flow channel.
  • 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.
  • the disposing step may further include at least one of fusing, curing, polymerizing and drying of at least one of the first and second porous electrode material. In some embodiments of the method of making a bipolar plate-electrode assembly, the disposing step may further include at least one of fusing, curing, polymerizing and drying the first porous electrode material and the second porous electrode material.
  • the present disclosure provides a bipolar plate-electrode assembly including:
  • a 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 includes at least one first flow channel, allowing fluid flow in the x-y plane of the bipolar plate electrode assembly, wherein the at least one first flow channel is in fluid
  • the second major surface includes at least one second flow channel, allowing fluid flow in the x-y plane of the bipolar plate electrode assembly, wherein 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 flow plate substrate; and an electrically conductive region disposed between the at least one first flow channel and the at least one second flow channel and intersecting the channel bottom of the at least one first flow channel and the channel bottom of the at least one second flow channel;
  • first porous electrode material contained in at least a portion of the at least one first flow channel, wherein the first porous electrode material is in electrical communication with the electrically conductive region through the at least one first flow channel bottom;
  • a second porous electrode material contained in at least a portion of the at least one second flow channel, wherein the second porous electrode material is in electrical communication with the electrically conductive region through the at least one second flow channel bottom;
  • first electrically conductive region is impervious to fluid and wherein the bipolar 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 present disclosure provides a bipolar plate-electrode assembly according to the first embodiment, wherein the electrically conductive region includes at least one of (i) an electrically conductive material having the same composition as that of the flow plate substrate, wherein the electrically conductive material is in electrical communication with the first and second porous electrode materials; and (ii) at least one via in the flow plate substrate and an electrically conductive material contained in at least a portion of the at least one via, wherein the electrically conductive material is in electrical communication with the first and second porous electrode materials.
  • the present disclosure provides a bipolar plate-electrode assembly according to the second embodiment, wherein the electrically conductive material includes at least one of a metal material, electrically conductive carbon, electrically conductive polymer and electrically conductive polymer composite.
  • the present disclosure provides a bipolar plate-electrode assembly according to the third 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 third or fourth embodiments, wherein the electrically conductive carbon includes at least one of glass like carbon, amorphous carbon, graphene, graphite, carbon dendrites, carbon nanotubes and branched carbon nanotubes.
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the third through fifth embodiments, wherein the electrically conductive polymer includes at least one of polyaniline, polypyrrole and polyacetylene.
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the third through sixth embodiments, wherein the electrically conductive polymer composite includes a polymer and an electrically conductive particulate.
  • the present disclosure provides a bipolar plate-electrode assembly according to the seventh embodiment, 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 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
  • the present disclosure provides a bipolar plate-electrode assembly according to the seventh or eighth 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 ninth embodiments, wherein the flow plate substrate is an electrically conductive flow plate substrate.
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the first through ninth embodiments, wherein the flow plate substrate is a dielectric flow plate substrate and the electrically conductive region includes at least one via in the flow plate substrate and an electrically conductive material contained in at least a portion of the at least one via, wherein the electrically conductive material is in electrical communication with the first and second porous electrode materials.
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the second through eleventh embodiments, wherein the at least one via includes a plurality of vias.
  • the present disclosure provides a bipolar plate-electrode assembly according to the eleventh or twelfth embodiments, wherein the dielectric flow plate substrate includes at least one dielectric polymer.
  • the present disclosure provides a bipolar plate-electrode assembly according to the thirteenth 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, styrene
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the eleventh through fourteenth embodiments, wherein 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 present disclosure provides a bipolar plate-electrode assembly according to any one of the eleventh through fourteenth embodiments, wherein the electrically conductive material includes at least one of a metal sheet, a metal pin and a plurality of metal pins.
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the first through sixteenth 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 seventeenth embodiment, wherein the electrically conductive carbon particulate of the at least one of the first porous electrode material and second porous electrode material 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 eighteenth embodiments, wherein the 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 nineteenth embodiments further comprising a first ion permeable membrane disposed adjacent the first major surface of the flow plate substrate.
  • the present disclosure provides a bipolar plate-electrode assembly according to any one of the first through twentieth embodiments further comprising a first discontinuous transport protection layer in contact with the first major surface of the flow plate substrate.
  • the present disclosure provides a bipolar plate- electrode assembly according to any one of the first through twenty-first embodiments further comprising a second ion permeable membrane disposed adjacent the second major surface of the fl ow pi ate sub strate .
  • the present disclosure provides a bipolar plate- electrode assembly according to any one of the first through twenty-second embodiments further comprising a second discontinuous transport protection layer in contact with the second major surface of the flow plate substrate.
  • the present disclosure provides a method of making a bipolar plate-electrode assembly including:
  • the second major surface includes at least one second flow channel, allowing fluid flow in the x-y plane of the bipolar plate electrode assembly, wherein 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 flow plate substrate; and an electrically conductive region disposed between the at least one first flow channel and the at least one second flow channel and intersecting the channel bottom of the at least one first flow channel and the channel bottom of the at least one second flow channel, (ii) disposing a first porous electrode material in at least a portion of the at least one first flow channel, and
  • the present disclosure provides an electrochemical cell stack for a liquid flow battery comprising at least one bipolar plate-electrode assembly according to any one of the first through twenty -third 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 twenty -third embodiments, wherein a half cell from each of the two electrochemical cells each includes a portion of the bipolar plate-electrode assembly.
  • the present disclosure provides an electrochemical cell stack for a liquid flow battery according to the twenty-sixth embodiment, wherein the electrode of at least one of the half cells that includes a portion of the bipolar plate-electrode assembly consists essentially of the porous electrode material.
  • the present disclosure provides a liquid flow battery comprising at least one bipolar plate-electrode assembly according to any one of the first through twenty -third embodiments.
  • 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 first through twenty-third embodiments, wherein a half cell from each of the two electrochemical cells each includes a portion of the bipolar plate-electrode assembly.
  • the present disclosure provides a liquid flow battery according to the twenty -ninth embodiment, wherein the electrode of at least one of the half cells that includes a portion of the bipolar plate-electrode assembly consists essentially of the porous electrode material.
  • a bipolar polar-electrode assembly was placed between two graphite plates of a test cell.
  • the flow plates of the test cell were commercially available quad serpentine flow channel with 25 cm 2 active area, available from Fuel Cell Technologies, Albuquerque, New Mexico.
  • the smooth side of the graphite plates were facing the sample, and a 127 micron thick gasket around the perimeter of the bipolar plate electrode assembly. They were then pressed together by torqueing the bolts to 110 in-lbs torque, compressing the bipolar plate- electrode assembly between the graphite plates.
  • power supply TDK - Lambda ZUP 10-40 a constant 35 A current was applied across the sample, and the voltage between the two plates was measured using a KEITHLEY 197 A Autoranging microvolt DMM.
  • An electrode solution was prepared as follows. Distilled Water, 49 grams, was poured into a beaker with a TEFLON coated magnetic stir bar. The beaker was placed on a magnetic stir plate and the plate was turned on to a medium setting. 0.5 grams of a mixture of 50% CNT, 40% ANS, and 10% TREVIRA 255, was added to the beaker and allowed to mix for a minimum of 30 sec to disperse the fibers into the water, producing Electrode Solution 1. Flow Plate Substrate 1 Preparation
  • Flow Plate Substrate 1 was made by machining a 3.0mm thick ACRYLITE® GP cell cast acrylic sheet (Evonik Cyro LLC, Evonik Industries AG Essen Germany). The machining was done using standard CNC machine tools. The flow plate substrate was machined on both major surfaces such that the channel features were registered to one another, i.e. the channel walls and channel bottoms were adjacent and registered with one another. The resultant flow fields of the flow plate substrate had the following dimensions after machining on both major surfaces.
  • 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.
  • a Buchner funnel was mounted to a 2000 ml vacuum flask.
  • a 110 mm diameter filter paper (WHATMAN CAT No. 1450-110, GE Healthcare Life Science) was placed in the Buchner funnel.
  • a 71 mm x 63 mm x 0.05 mm TEFLON sheet was placed in the center of the Buchner funnel on top of the filter paper.
  • the Teflon sheet had slits cut in many areas so water could be pulled through the sheet.
  • Flow Plate Substrate 1 was cut into a rectangle, 71 mm x 63 mm, with the flow field channels centered within the rectangle and placed on the TEFLON sheet.
  • the TEFLON sheet allowed the final bipolar plate-electrode assembly to be removed from the apparatus without damaging the electrode.
  • the flow plate substrate was oriented so the second silicone sheet completely covered the edges of the flow plate substrate.
  • the second silicone sheet held the electrode solution in place while the water was pulled through Flow Plate Substrate 1.
  • Electrode Solution 1 was then poured into the rectangular cutout of the second silicone sheet and vacuum was applied to the funnel. The water from Electrode Solution 1 was pulled through the layers and out of the funnel, leaving the solids of Electrode Solution 1 within the channels of the flow plate substrate.
  • the coated flow plate substrate was then removed and turned over and the procedure repeated to coat the flow channels on the opposite side of Flow Plate Substrate 1.
  • the sample was then pressed using a laminator at a temperature of 130°C, and then placed in an oven to dry at 130°C overnight with a 1.6 Kg weight on it, producing a bipolar plate-electrode assembly, Example 1. Using the Effective Electrode Resistance Measurement test, described above, the voltage measured across Example 1 was 0.642 volts.

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Abstract

La présente invention concerne des ensembles d'électrodes à plaque bipolaires et des empilements de cellules électrochimiques et des batteries à écoulement liquide fabriquées à partir de ces derniers. Les ensembles d'électrodes à plaque bipolaires comprennent un substrat de plaque d'écoulement ayant une première surface principale et une seconde surface principale opposée ; la première surface principale comprend au moins un premier canal d'écoulement et la seconde surface principale comprend au moins un second canal d'écoulement, permettant un écoulement de fluide dans le plan x-y de l'ensemble d'électrode à plaque bipolaire et une région électriquement conductrice disposée entre ledit premier canal d'écoulement et ledit second canal d'écoulement ; un premier et un second matériau d'électrode poreux contenus dans au moins une partie dudit premier canal d'écoulement et au moins une partie du second canal d'écoulement, respectivement, les premier et second matériaux d'électrode poreux étant en communication électrique avec la région électriquement conductrice à travers les fonds des canaux d'écoulement.
PCT/US2017/065957 2016-12-13 2017-12-13 Ensembles d'électrodes à plaque bipolaires et empilements de cellules électrochimiques et batteries à écoulement liquide à partir de ces derniers WO2018111962A1 (fr)

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CN111697248A (zh) * 2020-06-22 2020-09-22 内蒙古中科四维热管理材料有限公司 金属复合石墨双极板及制备方法
DE102020128043A1 (de) 2020-10-26 2022-04-28 Audi Aktiengesellschaft Bipolarplatte mit integriertem Kühlmittelkanal

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Publication number Priority date Publication date Assignee Title
CN111697248A (zh) * 2020-06-22 2020-09-22 内蒙古中科四维热管理材料有限公司 金属复合石墨双极板及制备方法
DE102020128043A1 (de) 2020-10-26 2022-04-28 Audi Aktiengesellschaft Bipolarplatte mit integriertem Kühlmittelkanal

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