WO2022082015A1 - Membrane-less redox flow electrical energy storage batteries - Google Patents

Membrane-less redox flow electrical energy storage batteries Download PDF

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Publication number
WO2022082015A1
WO2022082015A1 PCT/US2021/055240 US2021055240W WO2022082015A1 WO 2022082015 A1 WO2022082015 A1 WO 2022082015A1 US 2021055240 W US2021055240 W US 2021055240W WO 2022082015 A1 WO2022082015 A1 WO 2022082015A1
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Prior art keywords
redox flow
electrode
energy storage
electrical energy
battery
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PCT/US2021/055240
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French (fr)
Inventor
Ryan REDFORD
Norman P. SOLOWAY
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Redford Ryan
Soloway Norman P
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Priority to CN202180071082.7A priority Critical patent/CN116670867A/en
Publication of WO2022082015A1 publication Critical patent/WO2022082015A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/02—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof using combined reduction-oxidation reactions, e.g. redox arrangement or solion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
    • H01G11/18—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors against thermal overloads, e.g. heating, cooling or ventilating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/66—Current collectors
    • H01G11/70—Current collectors characterised by their structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H01M12/085—Zinc-halogen cells or batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/668—Composites of electroconductive material and synthetic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0221—Organic resins; Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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 relates to redox flow electrical energy storage batteries and more particularly to improvements in redox flow electrical energy batteries.
  • Redox flow electrical energy storage batteries exhibit high energy conversion efficiency, flexible design, high energy storage capacity, flexible location, deep discharge, high safety, environmental friendliness and low maintenance cost compared to other types of electrical energy storage systems, and are being adopted for various uses including renewable electrical energy storage for wind energy, solar energy and tidal energy installations, emergency energy supply systems, standby power systems, and load leveling for conventional electrical power supply systems.
  • Fig.1 shows a side elevational view, in partial cross-section, and Fig.2 a cross- sectional view along line II - II of a conventional dual electrode redox flow electrical energy storage battery system 10 made in accordance with the prior art.
  • the conventional redox flow electrical energy storage battery includes a pair of half-cells 12, 14 separated by a porous membrane 16.
  • An anolyte electrolyte 18 is flowed through half cell 12, and a catholyte electrolyte 20 is flowed through half cell 14.
  • An anode electrode 22 is located in half cell 12 and a cathode electrode 24 is located in half cell 14. Electrodes 22 and 24 are in turn in contact with anolyte electrolytes 18 and catholyte electrolyte 20 respectively.
  • Anode electrode 22 and cathode electrode 24 are connected to a source or load 26.
  • Analyte electrolyte 18 and catholyte electrolyte 20 are introduced into and flowed through half cells 12 and 14, respectively via conduits 28 and 30, respectively, and withdrawn from half cells 12 and 14 via conduits 32 and 34, respectively, such that redox reactions occur at the surfaces of electrodes 22 and 24.
  • electrolyte circulating pumps, electrolyte storage tanks, and valves are omitted.
  • Common problems in conventional redox flow electrical energy storage batteries include the presence of shunt currents within and between cells as fluid pressure drops across the half cells.
  • electrolyte concentration variations as electrolyte is depleted as electrolyte flows through the half cells results in decreased efficiency.
  • One method employed by prior art to manage shunt current variations involves providing long, small cross-section flow channels.
  • long, small cross-section flow channels create high electrical resistance from one end of the channel to the other thereby reducing shunt currents.
  • Long, small cross-section flow channels also result in pressure increases which increase pumping requirements and system flow pressure.
  • conventional dual electrode redox flow electrical energy storage batteries typically employ “activated” titanium electrodes which have a metallic coating to enhance initiation of the plating cycle which limits the battery’s operation and requires electrode reimbursement.
  • the requirement for a porous membrane adds to the cost of the battery system.
  • the porous membrane increases the volume and also increases spacing between the electrodes which reduces electric fields (V/m) and increases ion drift distance, thus further reducing battery performance.
  • the membrane-less flow battery in accordance with the our prior aforesaid PCT application includes a high surface area porous silicon electrode formed by a subtractive technique by subjecting a silicon substrate material to electrochemical etching to form interconnected nano structures or through holes or pores through the silicon substrate material. Surfaces of the porous silicon substrate material are then treated to enhance surface ion conductivity by deposition of a metal, preferably, titanium metal to form titanium silicide on surfaces of the pores of the silicon substrate material.
  • the titanium metal is deposited on the porous silicon substrate material using various deposition techniques including but not limited to chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), thermal CVD, electroplating, electroless plating, and/or solution deposition techniques, which are given as exemplary, and the metal-coating on the porous silicon substrate material is converted to the corresponding metal silicide by heating.
  • CVD chemical vapor deposition
  • PECVD plasma-enhanced chemical vapor deposition
  • thermal CVD thermal CVD
  • electroplating electroless plating
  • electroless plating electroless plating
  • solution deposition techniques which are given as exemplary
  • Tungsten metal also may be deposited on the porous silicon substrate material to form tungsten silicide coated electrodes.
  • the resulting substrate is a porous silicon substrate which includes a metallurgically bonded surface layer of metal silicide on the walls of the porous structure, which may be used as an electrode in a membrane-free redox flow energy storage battery.
  • an electrode for a flow battery is formed using an inkjet printer to form capillary flow channels on the surface of a metal or metal foil substrate. The resulting substrates are then stacked to form a flow battery electrode.
  • capillary flow channels may be formed on a metal or metal foil substrate by molding.
  • capillary flow channels are formed on silicon wafers using a two step patterning/etching technique. The resulting patterned wafers are then stacked to form a flow battery electrode.
  • Fig. l is a side view, in partial cross-section, of a conventional dual electrode redox flow electrical storage battery system
  • Fig. 3 is a schematic block diagram of a process for producing an electrode for use in a membrane-less redox flow energy storage battery in accordance with one embodiment of the present disclosure
  • Figs. 4A-4B are cross-sectional views of an electrode formed by the process of Fig. 3 at various stages of production in accordance with the present disclosure
  • Fig. 5 is a schematic block diagram of a process for producing an electrode for use in a membrane-less redox flow electrical energy storage battery in accordance with another embodiment of the present disclosure
  • Figs. 6A-6O are cross-sectional views of an electrode formed by the process of Fig. 5 at various stages of production in accordance with the present disclosure.
  • Figs. 7-10 are cross-sectional views of flow batteries made in accordance with the present disclosure.
  • the process starts with a metal foil or substrate 40 in which through holes 42 are punched or drilled.
  • Patterned capillary flow channels 44 are then formed on one side of the substrate 40 by inkjet printing lines of material 46 such as an epoxy such as benzyocyclobutene (BCB), polyimide (PI), bismaleimide (BMI) or other acid resistant material, at a printing step 50.
  • the metal foil or substrate is about 1000 microns thick, while the lines of material 46 are deposited to a thickness of about 400 microns. Lines 46 may be separated by about 1400 microns.
  • the deposited material 46 typically is permanently fixed to the substrate 10 in a baking step.
  • a plurality of patterned substrates are then stacked in a stacking step 54 to form a flow battery electrode 18 with straight (See Fig. 4A) or staggered (Fig. 4B) capillary flow passages which may then be incorporated into a redox flow battery as will be described below.
  • FIGs. 5 and 6A-6O there is illustrated an alternative process for forming an electrode in accordance with the present disclosure.
  • the overall process is as follows: starting with a nitride layer coated silicon substrate, a mask pattern 102 is formed on the nitride layer at a patterning step.
  • the patterned silicon substrate is then subjected to a wet etch at a first etching step to remove unprotected areas of the silicon nitride layer.
  • the mask layer is then stripped in a first stripping step, and the exposed silicon areas are subjected to a first etching to form a shallow channel
  • the resulting silicon substrate is then patterned with a resist at a masking step which covers the walls of channel and selected areas of the nitride layer, and subjected to a shallow etch at etching step which removes the exposed areas of the nitride layer.
  • the resist is then stripped in a second stripping step and the resulting silicon substrate subjected to a further deep wet etch blend trenches at a further etching step.
  • the remaining nitride layer is then stripped at a stripping step and the resulting contoured substrate is then cleaned prior to deposition of a dielectric layer on the side exposed surfaces (other than the bottom surfaces) of the etched blind trenches in a jet field coating step.
  • the bottoms of the etched blind trenches are then printed with a silver nanoparticle ink for providing a seed for electrolysis or traditional nickel or zinc plating.
  • the resulting structure is then electroplated at electroplating step, and an inkjet is then used to selectively apply lines of bonding adhesive so that the resulting contoured wafers may then be bonded one on top of another whereby to create capillary flow channels.
  • Fig. 7 shows a membrane-less redox flow electrical energy storage battery 160 in accordance with the present disclosure.
  • Battery 160 includes a case 162 an anode electrode 164 in the form of a metal plate electrode formed as above described with reference to Figs. 3 and 4, and a cathode electrode 166 formed, for example, of graphite.
  • Anode 164 and cathode 166 are connected to a load 170.
  • a zinc/halide containing electrolyte 174, for example, zinc/bromide is flowed form a reservoir 176 through the battery 160.
  • Electrolyte 174 also may comprise zinc/iodide.
  • the zinc bromide is dissociated and the positive zinc ions move into the anode electrode, and the negative bromide ions move into the positive zinc ions.
  • the positive zinc ions move from the anode electrode and the bromide ions move from the cathode electrode reforming zinc bromide while the electrons flow through the external circuit in the same direction.
  • the reverse occurs and the zinc bromide is dissociated, with the zinc ions and the electrons moving back into the anode electrode and he bromide ions moving back into the cathode net higher energy stake.
  • the anode may be made physically larger, i.e., thicker than the cathode.
  • the increased thickness porous structure of the anode allows protons more time to move into the electrode matrix. Also, less electrolyte is required for similar energy storage. And, since the protons move more slowly into the anode, this permits a faster charge and discharge rate without a danger of fractures or pulverization of the electrode.
  • Fig. 10 an alternative form of membrane-less redox flow electrical energy storage battery 200 is shown.
  • Battery 200 is similar to battery 160 shown in Fig. 7, and includes a case 202, anode electrode 204 and cathode electrode 206. However, in the Fig.
  • cathode 206 comprises a solid metal or carbon substrate 208 covered with a silicon wafer electrode 210 formed as above discussed with reference to Figs. 5 and 6, facing the electrolyte 212.
  • the anode may comprise a silicon wafer electrode of Figs. 5 and 6 as described above.
  • electrolyte 214 such as, for example, zinc/bromide is flowed from a reservoir 216 through the battery 200.
  • Battery 200 operates similarly to battery 160 described above with positive zinc ions moving into and out of the anode electrode 204, and bromide ions moving into and out of the cathode electrode 206.

Abstract

A membrane-less redox flow electrical energy storage battery, comprising a cathode electrode and an anode electrode, wherein the cathode electrode or the anode electrode comprise a solid metal or carbon electrode covered at least in part by a substrate element having capillary flow channels, formed on or in the substrate element; and an electrolyte.

Description

MEMBRANE-LESS REDOX FLOW ELECTRICAL ENERGY STORAGE BATTERIES The present invention relates to redox flow electrical energy storage batteries and more particularly to improvements in redox flow electrical energy batteries. Redox flow electrical energy storage batteries exhibit high energy conversion efficiency, flexible design, high energy storage capacity, flexible location, deep discharge, high safety, environmental friendliness and low maintenance cost compared to other types of electrical energy storage systems, and are being adopted for various uses including renewable electrical energy storage for wind energy, solar energy and tidal energy installations, emergency energy supply systems, standby power systems, and load leveling for conventional electrical power supply systems. Fig.1 shows a side elevational view, in partial cross-section, and Fig.2 a cross- sectional view along line II - II of a conventional dual electrode redox flow electrical energy storage battery system 10 made in accordance with the prior art. The conventional redox flow electrical energy storage battery includes a pair of half-cells 12, 14 separated by a porous membrane 16. An anolyte electrolyte 18 is flowed through half cell 12, and a catholyte electrolyte 20 is flowed through half cell 14. An anode electrode 22 is located in half cell 12 and a cathode electrode 24 is located in half cell 14. Electrodes 22 and 24 are in turn in contact with anolyte electrolytes 18 and catholyte electrolyte 20 respectively. Anode electrode 22 and cathode electrode 24 are connected to a source or load 26. Analyte electrolyte 18 and catholyte electrolyte 20 are introduced into and flowed through half cells 12 and 14, respectively via conduits 28 and 30, respectively, and withdrawn from half cells 12 and 14 via conduits 32 and 34, respectively, such that redox reactions occur at the surfaces of electrodes 22 and 24. For ease of illustration, electrolyte circulating pumps, electrolyte storage tanks, and valves are omitted. Common problems in conventional redox flow electrical energy storage batteries include the presence of shunt currents within and between cells as fluid pressure drops across the half cells. Also, electrolyte concentration variations as electrolyte is depleted as electrolyte flows through the half cells results in decreased efficiency. One method employed by prior art to manage shunt current variations involves providing long, small cross-section flow channels. However, long, small cross-section flow channels create high electrical resistance from one end of the channel to the other thereby reducing shunt currents. Long, small cross-section flow channels also result in pressure increases which increase pumping requirements and system flow pressure.
Furthermore, conventional dual electrode redox flow electrical energy storage batteries typically employ “activated” titanium electrodes which have a metallic coating to enhance initiation of the plating cycle which limits the battery’s operation and requires electrode reimbursement.
Also, in conventional dual electrode redox flow electrical energy storage batteries, uniformity of the electrical field across the electrolyte is limited by technical challenges associated with solid metal electrode integration and design, control of their separate operation, and electrode shape. Further complicating operation and operation effectiveness of conventional dual electrode redox flow electrical energy storage batteries is the fact that plating uniformity is impacted by the chemical stoichiometry which will vary with interactions within the flowing field. Thus, rate of plating and generation of secondary chemistry is non-uniform due to the varying chemical distribution resulting in variations in laminar flow effects across the electrodes, relative to the input and output fluid ports.
Moreover, the requirement for a porous membrane adds to the cost of the battery system. Also, the porous membrane increases the volume and also increases spacing between the electrodes which reduces electric fields (V/m) and increases ion drift distance, thus further reducing battery performance.
In our prior PCT Application Serial No. PCT/US2020/027940, we propose improvements over conventional dual electrode redox flow electrical energy storage battery systems by providing a membrane-less redox flow battery system. The membrane-less flow battery in accordance with the our prior aforesaid PCT application includes a high surface area porous silicon electrode formed by a subtractive technique by subjecting a silicon substrate material to electrochemical etching to form interconnected nano structures or through holes or pores through the silicon substrate material. Surfaces of the porous silicon substrate material are then treated to enhance surface ion conductivity by deposition of a metal, preferably, titanium metal to form titanium silicide on surfaces of the pores of the silicon substrate material. The titanium metal is deposited on the porous silicon substrate material using various deposition techniques including but not limited to chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), thermal CVD, electroplating, electroless plating, and/or solution deposition techniques, which are given as exemplary, and the metal-coating on the porous silicon substrate material is converted to the corresponding metal silicide by heating. Tungsten metal also may be deposited on the porous silicon substrate material to form tungsten silicide coated electrodes.
According to our aforesaid PCT application, the resulting substrate is a porous silicon substrate which includes a metallurgically bonded surface layer of metal silicide on the walls of the porous structure, which may be used as an electrode in a membrane-free redox flow energy storage battery.
The present disclosure also provides a low cost additive process for producing electrodes for use in a redox flow electrical energy storage batteries. In accordance with one embodiment of the disclosure, an electrode for a flow battery is formed using an inkjet printer to form capillary flow channels on the surface of a metal or metal foil substrate. The resulting substrates are then stacked to form a flow battery electrode. Alternatively, capillary flow channels may be formed on a metal or metal foil substrate by molding. In yet another alternative embodiment, capillary flow channels are formed on silicon wafers using a two step patterning/etching technique. The resulting patterned wafers are then stacked to form a flow battery electrode.
Further features and advantages of the present disclosure will be seen from the following detailed description, taken in conjunction with the accompanying drawings, wherein like numerals depict like parts, and wherein:
Fig. l is a side view, in partial cross-section, of a conventional dual electrode redox flow electrical storage battery system;
Fig. 2 of the prior art dual electrode redox flow electrical energy storage battery system of Fig 1;
Fig. 3 is a schematic block diagram of a process for producing an electrode for use in a membrane-less redox flow energy storage battery in accordance with one embodiment of the present disclosure;
Figs. 4A-4B are cross-sectional views of an electrode formed by the process of Fig. 3 at various stages of production in accordance with the present disclosure; Fig. 5 is a schematic block diagram of a process for producing an electrode for use in a membrane-less redox flow electrical energy storage battery in accordance with another embodiment of the present disclosure;
Figs. 6A-6O are cross-sectional views of an electrode formed by the process of Fig. 5 at various stages of production in accordance with the present disclosure; and
Figs. 7-10 are cross-sectional views of flow batteries made in accordance with the present disclosure.
Referring to Figs. 3 and 4A, the process starts with a metal foil or substrate 40 in which through holes 42 are punched or drilled. Patterned capillary flow channels 44 are then formed on one side of the substrate 40 by inkjet printing lines of material 46 such as an epoxy such as benzyocyclobutene (BCB), polyimide (PI), bismaleimide (BMI) or other acid resistant material, at a printing step 50. Typically the metal foil or substrate is about 1000 microns thick, while the lines of material 46 are deposited to a thickness of about 400 microns. Lines 46 may be separated by about 1400 microns. The deposited material 46 typically is permanently fixed to the substrate 10 in a baking step.
A plurality of patterned substrates are then stacked in a stacking step 54 to form a flow battery electrode 18 with straight (See Fig. 4A) or staggered (Fig. 4B) capillary flow passages which may then be incorporated into a redox flow battery as will be described below.
Referring to Figs. 5 and 6A-6O, there is illustrated an alternative process for forming an electrode in accordance with the present disclosure.
The overall process is as follows: starting with a nitride layer coated silicon substrate, a mask pattern 102 is formed on the nitride layer at a patterning step. The patterned silicon substrate is then subjected to a wet etch at a first etching step to remove unprotected areas of the silicon nitride layer. The mask layer is then stripped in a first stripping step, and the exposed silicon areas are subjected to a first etching to form a shallow channel
The resulting silicon substrate is then patterned with a resist at a masking step which covers the walls of channel and selected areas of the nitride layer, and subjected to a shallow etch at etching step which removes the exposed areas of the nitride layer. The resist is then stripped in a second stripping step and the resulting silicon substrate subjected to a further deep wet etch blend trenches at a further etching step.
The remaining nitride layer is then stripped at a stripping step and the resulting contoured substrate is then cleaned prior to deposition of a dielectric layer on the side exposed surfaces (other than the bottom surfaces) of the etched blind trenches in a jet field coating step. The bottoms of the etched blind trenches are then printed with a silver nanoparticle ink for providing a seed for electrolysis or traditional nickel or zinc plating. The resulting structure is then electroplated at electroplating step, and an inkjet is then used to selectively apply lines of bonding adhesive so that the resulting contoured wafers may then be bonded one on top of another whereby to create capillary flow channels.
Fig. 7 shows a membrane-less redox flow electrical energy storage battery 160 in accordance with the present disclosure. Battery 160 includes a case 162 an anode electrode 164 in the form of a metal plate electrode formed as above described with reference to Figs. 3 and 4, and a cathode electrode 166 formed, for example, of graphite. Anode 164 and cathode 166 are connected to a load 170. A zinc/halide containing electrolyte 174, for example, zinc/bromide is flowed form a reservoir 176 through the battery 160. Electrolyte 174 also may comprise zinc/iodide.
Referring to Figs. 8 and 9 during charging the zinc bromide is dissociated and the positive zinc ions move into the anode electrode, and the negative bromide ions move into the positive zinc ions. During discharge, the positive zinc ions move from the anode electrode and the bromide ions move from the cathode electrode reforming zinc bromide while the electrons flow through the external circuit in the same direction. When the cell is recharged, the reverse occurs and the zinc bromide is dissociated, with the zinc ions and the electrons moving back into the anode electrode and he bromide ions moving back into the cathode net higher energy stake.
A feature an advantage of the present disclosure is that the anode may be made physically larger, i.e., thicker than the cathode. The increased thickness porous structure of the anode allows protons more time to move into the electrode matrix. Also, less electrolyte is required for similar energy storage. And, since the protons move more slowly into the anode, this permits a faster charge and discharge rate without a danger of fractures or pulverization of the electrode. Referring to Fig. 10 an alternative form of membrane-less redox flow electrical energy storage battery 200 is shown. Battery 200 is similar to battery 160 shown in Fig. 7, and includes a case 202, anode electrode 204 and cathode electrode 206. However, in the Fig. 10 embodiment, cathode 206 comprises a solid metal or carbon substrate 208 covered with a silicon wafer electrode 210 formed as above discussed with reference to Figs. 5 and 6, facing the electrolyte 212. Alternatively, the anode may comprise a silicon wafer electrode of Figs. 5 and 6 as described above. As before, electrolyte 214 such as, for example, zinc/bromide is flowed from a reservoir 216 through the battery 200. Battery 200 operates similarly to battery 160 described above with positive zinc ions moving into and out of the anode electrode 204, and bromide ions moving into and out of the cathode electrode 206.

Claims

Claims:
1. A membrane-less redox flow electrical energy storage battery, comprising: a cathode electrode and an anode electrode, wherein the cathode electrode or the anode electrode comprise a solid metal or carbon electrode covered at least in part by a substrate element having capillary flow channels/formed on or in the substrate; and an electrolyte.
2. The redox flow battery of claim 1, wherein the flow capillary channels are built up on a surface of the substrate element.
3. The redox flow battery of claim 1, wherein the flow capillary channels are formed below the surface of the substrate element.
4. The redox flow battery of claim 1, comprising a plurality of metal electrodes in a stack.
5. The redox flow battery of claim 4, wherein the plurality of said metal electrodes are adhesively bonded to one another in said stack.
6. The redox flow batter of claim 1, wherein solid metal electrodes comprise metal substrates and the capillary flow channels are formed on surfaces of said metal substrates by printing or molding built-up boundaries for said capillary flow channels.
7. The redox flow battery of claim 1, wherein the substrate element comprises a silicon substrate having patterned with capillary flow channels formed in one surface.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100119937A1 (en) * 2007-03-28 2010-05-13 Redflow Pty Ltd Cell stack for a flowing electrolyte battery
US20150294803A1 (en) * 2012-08-13 2015-10-15 Intel Corporation Energy storage devices with at least one porous polycrystalline substrate
US20180138568A1 (en) * 2015-05-11 2018-05-17 Bromine Compounds Ltd. An additive for a flow battery
WO2018111958A1 (en) * 2016-12-13 2018-06-21 3M Innovative Properties Company Bipolar plate-electrode assemblies and electrochemical cell stacks and liquid flow batteries therefrom
US20190131620A1 (en) * 2016-03-10 2019-05-02 3M Innovative Properties Company Electrode solutions and electrochemical cells and batteries therefrom

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100119937A1 (en) * 2007-03-28 2010-05-13 Redflow Pty Ltd Cell stack for a flowing electrolyte battery
US20150294803A1 (en) * 2012-08-13 2015-10-15 Intel Corporation Energy storage devices with at least one porous polycrystalline substrate
US20180138568A1 (en) * 2015-05-11 2018-05-17 Bromine Compounds Ltd. An additive for a flow battery
US20190131620A1 (en) * 2016-03-10 2019-05-02 3M Innovative Properties Company Electrode solutions and electrochemical cells and batteries therefrom
WO2018111958A1 (en) * 2016-12-13 2018-06-21 3M Innovative Properties Company Bipolar plate-electrode assemblies and electrochemical cell stacks and liquid flow batteries therefrom

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