Classifications

• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
  • H01G11/54—Electrolytes
  • H01G11/58—Liquid electrolytes
• • 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
  • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
  • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
• • 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
  • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M6/00—Primary cells; Manufacture thereof
  • H01M6/24—Cells comprising two different electrolytes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M6/00—Primary cells; Manufacture thereof
  • H01M6/30—Deferred-action cells
  • H01M6/32—Deferred-action cells activated through external addition of electrolyte or of electrolyte components
• • 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
  • H01M8/08—Fuel cells with aqueous electrolytes
  • H01M8/083—Alkaline fuel cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
  • H01M8/184—Regeneration by electrochemical means
  • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0002—Aqueous electrolytes
  • H01M2300/0014—Alkaline electrolytes
• • 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

• Liquid batteries whether flow or no-flow, are known in the art and work on the same principles as solid batteries, except the electrolyte is liquid.
• Such batteries are comprised of electrochemical cells which are based on reduction-oxidation chemistry. Oxidation occurs on the anode side of the cell and reduction on the cathode side.
• the solvents used in electrochemical cells are varied. In many circumstances, aqueous solutions are used on both sides of an electrochemical cell with each side (cathode side and anode side) in contact with an electrode (i.e., the cathode and anode respectively). The electrodes of the two-half cells are placed in electrical contact to allow for current to flow. To maintain charge balance, an electrochemical cell must also allow for the passage of ions.
• Electrochemical cells deploy membranes or salt bridges to prevent shorting and to separate multiple electrolyte solutions. Such membranes are costly and readily degrade over time.
• WO2017/106215 reports electrochemical cells which may be used in the absence of membranes and which use two or more immiscible electrolytes.
• the present disclosure includes improved designs for electrochemical cells and batteries (including flow cells and flow batteries) that, in certain embodiments, include a single electrolyte solution, an anode, a current collector, and a porous, non-conductive spacer between the current collector and anode. In contrast to typical flow batteries, the anode and current collector in such embodiments need not be immersed in an electrolyte. Additional embodiments include improved designs for membraneless electrochemical cells and batteries that comprise multiple electrolytes.
• Embodiments of the disclosure include electrochemical cells and batteries that can operate with a single electrolyte solution.
• an electrochemical cell comprising an anode, a current collector and a porous, non-conductive spacer between the anode and the current collector is provided. Additional designs for electrochemical cells and batteries that can operate with a single electrolyte solution are also provided.
• an electrochemical battery comprising one or more of these electrochemical cells and further comprising a load is provided.
• Further embodiments include certain membraneless electrochemical cells that contain separate first and second electrolyte solutions at the cathode and anode, respectively; batteries comprising these electrochemical cells; methods of delivering hydrogen, electricity or both with the cells and batteries to applications; capacitors; and various methods related to these embodiments.
• FIG. 1 is a schematic of one embodiment of electrochemical cells of the disclosure.
• FIG. 2 is a schematic of one embodiment of an electrochemical battery of the disclosure.
• FIG. 3 is a schematic block diagram of an embodiment of an electrochemical cell according to the present disclosure.
• FIG. 4A is a schematic block diagram of an embodiment of an electrochemical cell according to the present disclosure.
• FIG. 4B is a schematic block diagram of an embodiment of an electrochemical cell according to the present disclosure.
• FIG. 5 is a schematic of an embodiment of an electrochemical cell of the disclosure.
• FIG. 6 is a schematic of an embodiment of an electrochemical cell of the disclosure.
• FIG. 7 is a schematic of an embodiment of an electrochemical cell of the disclosure.
• FIG. 8 is a schematic of an embodiment of an electrochemical cell of the disclosure in flow mode.
• FIG. 9 is a schematic of an embodiment of an electrochemical cell of the disclosure.
• Embodiments of the disclosure include electrochemical cells and batteries that can operate with a single electrolyte solution. Such cells and batteries do not require multiple electrolyte solutions separated by a membrane, by a salt bridge or by other techniques.
• an electrochemical cell comprising an anode, a current collector and a porous, non-conductive spacer between the anode and the current collector is provided.
• the electrochemical cells of the disclosure may be used to form batteries to supply electricity, hydrogen, or both to applications.
• Electrical applications include, for example, grid applications such as cell phone tower backup power or backup power for wind farms or solar farms.
• the electricity could also be used to power vehicles, household appliances, consumer goods or toys.
• the hydrogen may be delivered to an application such as a fuel cell for electricity production or a vehicle or to, for example, an engine or furnace for burning.
• the electrochemical cells may be configured such that electricity is primarily delivered, hydrogen is primarily delivered, or both are delivered in various ratios.
• the cells and batteries of the disclosure run in flow mode in that electrolyte is added to the cell or battery and then removed after use, thereby replenishing the supply of electrolyte to the cell or battery.
• the anode is in physical contact with the porous, non-conductive spacer, such as non-conductive screen, which in turn is in physical contact with the current collector such as carbon foam.
• the spacer is not in physical contact with the anode, the current collector, or both, but is instead positioned at a distance from the anode, current collector, or both.
• the purpose of the porous, non-conductive spacer is to prevent physical contact of the current collector with the anode.
• non-conductive with reference to the porous spacer means that the spacer is not electrically conductive.
• the spacer is porous to electrolyte, and is also porous in a non-selective manner to anions and cations in the electrolyte solution. Being electrically non-conductive, the porous spacer does not permit the passage of electrons through it. These features of the spacer differentiate it from salt bridges and membranes in conventional batteries, which are often used to maintain separation of multiple electrolyte solutions.
• Many different types of non-conductive porous materials can be used for the spacer, such as an organic polymer, surgical tape, fiberglass film, glass wool, wood, paper, cloth, cardboard, and nylon.
• One such organic polymer is vinyl coated polyester.
• the thickness of the spacer is often between about 0.1 mm and about 0.8 mm.
• a microporous material such as surgical tape, may be used to wrap the electrochemical cell so as to help maintain its physical integrity.
• the wrapping need not completely encase the electrochemical cell.
• Current collectors and anodes in electrochemical cells in this disclosure may be selected from suitable materials.
• suitable current collector materials include steel, carbon such as in the graphite allotrope of carbon, carbon impregnated with a metal, and carbon foam.
• Conducting carbon cloth (which is also referred to as carbon foam), for example, is a suitable current collector for many embodiments and is a conducting material.
• Suitable anodes for embodiments having a single electrolyte solution include metals in Column 13 of the Periodic Table and their alloys. These metals and alloys include, for example, aluminum, gallium, indium and thallium, as well as alloys comprising at least one of these.
• One example alloy has the name of Galinstan, which is an alloy of gallium, indium and tin.
• the electrochemical cell further comprises a single electrolyte solution.
• the electrochemical cell may be saturated with respect to the electrolyte.
• the cell is not immersed in an electrolyte bath.
• One example of a current collector is carbon foam.
• the electrolyte may be sprayed onto the cell until or before the carbon foam is saturated in such an example.
• additional electrolyte or other materials such as salts, oxidants, or bases
• a recirculator could be used to continuously recycle and deliver electrolyte or other materials to the cell.
• electrolyte or other materials to the cell.
• the anode of the electrochemical cell is made from aluminum, for example.
• the aluminum is in the form of a sheet. In many other embodiments it is in the form of a screen or other thin porous structure.
• the thickness of the aluminum screen may be, for example between about 0.05 mm and about 0.5 mm, or between about 0.1 mm and about 0.3 mm.
• the current collector can be carbon foam and the porous, non-conductive spacer can be a non-conductive screen such as an organic polymer or surgical tape.
• One such polymer is vinyl coated polyester.
• Additional embodiments include 1) an electrochemical cell comprising an anode, a current collector, a porous, non-conductive spacer between the anode and the current collector, and a single electrolyte solution; 2) an electrochemical cell consisting essentially of an anode, a current collector, a porous, non-conductive spacer between the anode and the current collector, and a single electrolyte solution; and 3) an electrochemical cell consisting of an anode, a current collector, a porous, non-conductive spacer between the anode and the current collector, and a single electrolyte solution.
• Electrochemical cells are often connected to one another by metal conductors to form electrochemical batteries.
• An example of a metal conductor is copper such as copper wire or wires.
• an aluminum anode on one electrochemical cell is in contact with a porous, non-conductive spacer on the cell and the spacer is in turn in contact with a carbon foam current collector.
• the aluminum anode is also in contact with a metal conductor to the current collector on an adjacent electrochemical cell, which in turn is in contact with its own porous, non-conductive spacer and corresponding aluminum anode.
• a series of electrochemical cells may be connected.
• the terminal electrochemical cells may be connected to a load, such as an application or to additional electrochemical cell series so that the overall electrochemical battery has both a series and parallel arrangement of electrochemical cells.
• the electrochemical cells are also configured to operate as flow cells.
• the cells may be configured as flow cells so as to support a flow battery, for example.
• electrolyte can be provided to cells during the operation of the battery continuously during operation so that electrical charging is not required.
• the electrolyte comprises water and one or more salts.
• solvents for use in the electrolyte including water and others, may be found in Table 1.
• the electrolyte there are two salts that are added to the electrolyte.
• examples of such salts include salts of peroxydi sulfate (such as sodium peroxydi sulfate), hypochlorite, and sulfate (such as sodium sulfate).
• the electrolyte may additionally comprise a base, such as sodium hydroxide.
• One of the salts is an oxidant.
• the electrolyte contains an oxidant and also contains an additional salt, such as a metal salt found in Table 3, wherein the anion portion of the metal salt and the oxidant differ.
• oxidant refers to the compound added to perform oxidation as well as the resulting anion that results from dissociation of that compound.
• peroxydisulfuric acid H 2 S 2 0 8
• sodium peroxydi sulfate Na 2 S 2 0 8
• the peroxydi sulfate anion S 2 0 8 2"
• the anion form is the form which acts to oxidize another species and which in turn is reduced.
• hypochlorite and other hypohalite compounds including NaCIO
• Hexavalent chromium compounds such as chromic and dichromic acids and chromium trioxide, pyridinium chlorochromate (PCC), and chromate/dichromate compounds
• Permanganate compounds such as potassium permanganate
• the other salt may be, for example, any one of the compounds found in Table 3.
• the second salt should be a compound that dissociates so as to produce a metal ion.
• a metal salt is sodium sulfate.
• the electrolyte further contains a base such as a strong base.
• strong bases include LiOH, RbOH, CsOH, Sr(OH) 2 , Ba(OH) 2 , NaOH, KOH, Ca(OH) 2 , or a combination thereof.
• strong bases include LiOH, RbOH, CsOH, Sr(OH) 2 , Ba(OH) 2 , NaOH, KOH, Ca(OH) 2 , or a combination thereof.
• strong bases include LiOH, RbOH, CsOH, Sr(OH) 2 , Ba(OH) 2 , NaOH, KOH, Ca(OH) 2 , or a combination thereof.
• NaOH NaOH.
• the electrolyte comprises one of water or an alcohol.
• the electrolyte can be a catholyte, for example.
• an oxidant and a metal salt are present in this electrolyte, the two can have different anion components.
• An example oxidant includes sodium peroxydi sulfate and an example metal salt is sodium sulfate.
• This electrolyte may further comprise a base, such as sodium hydroxide.
• a further embodiment includes an electrochemical cell comprising:
• the anode, current collector, and spacer may have one or more characteristics or features described above for those components. Such an embodiment may, for example, be constructed in one location then transported to another location where it is contacted with electrolyte (such as a single electrolyte solution) for use.
• electrolyte such as a single electrolyte solution
• the disclosure includes additional embodiments of electrochemical cells that can operate with a single electrolyte solution.
• an electrochemical cell comprising a single aqueous electrolyte solution in contact with a non-metallic current collector, an oxidant, and a metal solid wherein current travels from the metal solid to the current collector via a load, is provided.
• the electrolyte solution can be basic and the oxidant can be S 2 08 2" , for example.
• the electrolyte solution may further comprise, for instance, sodium hydroxide.
• Suitable metal solids include those in Column 13 of the Periodic Table and their alloys. These metals and alloys include, for example, aluminum, gallium, indium and thallium, as well as alloys comprising at least one of these.
• One example metal solid is aluminum, such as aluminum in the form of a foil.
• the cell may further comprise a porous stabilizer.
• the cell may comprise a metal sulfate (such as Na 2 S0 4 ) where the current collector is carbon foam and the porous stabilizer is glass wool or a borosilicate or both.
• the pH of the cell may, for example, be greater than 12, greater than 13 or greater than 14.
• Cells such as this which can use a single electrolyte solution, may produce, for example, between about 10 Watt-hours/(kg of electrolyte + anode metal) and about 680 Watt-hour s/(kg of electrolyte + anode metal).
• the cell When measured per kg of electrolyte, the cell may produce, for example, between about 10 Watt-hours/kg of electrolyte and about 100 Watt-hours/kg of electrolyte, between about 40 Watt-hours/kg of electrolyte and about 80 Watt-hours/kg of electrolyte, or between about 10 Watt-hours/kg of electrolyte and about 60 Watt-hours/kg of electrolyte.
• the power produced per square centimeter of metal solid can be, for example, between about 600 mW and about 1000 mW.
• the cell may be configured to operate in flow mode.
• the cell may include an inflow stream that comprises, for example, an aqueous electrolyte solution that may further comprise an oxidant such as sodium peroxydi sulfate or a solution comprising peroxydi sulfate anion or both.
• Oxidant (such as solid Na 2 S 2 0 8 or Na 2 S 2 0 8 in solution) can be provided to the cell, for example, Na 2 S 2 0 8 in an aqueous basic solution, where the base may be, for example, sodium hydroxide.
• the cell may further comprise an outflow stream.
• the outflow stream may comprise an aqueous solution and may also include, for example, metal sulfate.
• a further embodiment includes a method of creating a capacitor comprising the step of disconnecting the load from one side of an electrochemical cell of the disclosure that can operate using a single electrolyte solution. The method further comprises the step of reconnecting the load.
• a further embodiment includes a capacitor, prepared by the process of alternatively disconnecting and reconnecting the load from at least one of the current collector or anode in the electrochemical cell.
• An additional embodiment that can operate with a single electrolyte solution is an electrochemical cell comprising a single aqueous electrolyte solution in contact with a non-metallic current collector, an oxidant, and a metal solid wherein current travels from the metal solid to the current collector via a load, and wherein the pH is greater or equal to 12.
• the non-metallic current collector can be carbon foam
• the oxidant can be a peroxydi sulfate salt
• the metal solid can be aluminum.
• An additional embodiment that can operate with a single electrolyte solution is an electrochemical cell comprising a single aqueous electrolyte solution in contact with a non-metallic current collector, an oxidant, and one or more anodes wherein current travels from the one or more anodes to the current collector via a load, and wherein the pH is greater or equal to 10.
• Suitable anodes include metals in Column 13 of the Periodic Table and their alloys. These metals and alloys include, for example, aluminum, gallium, indium and thallium, as well as alloys comprising at least one of these.
• One example metal is aluminum, such as aluminum in the form of foil.
• the anodes can also be separated by an insulator. In some embodiments, the pH is greater or equal to 12.
• Example 7 An example of an electrochemical cell that can operate with a single electrolyte solution is provided in Example 7 and is illustrated in FIG. 9.
• An additional embodiment of the disclosure includes a method of making an electrochemical cell of the disclosure.
• the method comprises 1) providing an electrochemical cell comprising an anode, a current collector and a porous, non- conductive spacer between the anode and the current collector; and 2) contacting the cell with a single electrolyte solution.
• the cell can be contacted with electrolyte solution, for example, by spraying the electrolyte solution onto the cell.
• the electrolyte could also be applied in bulk such as by immersion.
• the electrolyte solution could also be applied to the cell as droplets via drip or as an atomized mist.
• the electrolyte can also be supplied in bulk compartments, or in any combinations of the techniques provided herein.
• a further embodiment includes a method, such as a method of operating an electrochemical cell in flow mode, that comprises 1) providing an electrochemical cell according to any of the embodiments above and that comprises a single electrolyte solution, 2) operating the cell to produce electricity, hydrogen, or both electricity and hydrogen (such as when the cell is connected to a load), and 3) providing additional electrolyte solution (or one or more components thereof) to the cell during its operation.
• Such an embodiment can further comprise 4) withdrawing spent electrolyte solution (or one or more components thereof) from the cell during its operation, for example, simultaneously with providing the additional electrolyte solution (or one or more components thereof) to the cell.
• the electrolyte solution in these embodiments may have any composition appropriate for the cells as described herein. Components of the electrolyte solution can include, for example, an oxidant, a metal salt, and a base.
• a further embodiment includes the method performed on a battery that comprises the cell.
• electrochemical batteries comprising electrochemical cells of the disclosure.
• An electrochemical battery contains one or more cells and is electrically connected to a load.
• the load could be the resistance in a wire or it could be to an application, or both.
• the electrochemical batteries of the disclosure may be used to generate electricity through the load, hydrogen, or both.
• the battery can be configured, for example, to favor electricity or hydrogen.
• Hydrogen production may be controlled by adjusting pH and the specific surface area of the anode. Starting with an alkaline solution, as the pH increases and the larger specific surface of the anode used, the more hydrogen produced. For example the surface area of the aluminum may be increase by folding over an aluminum screen multiple times. Electricity may be favored when oxidant concentration is increased and the solution is made increasingly alkaline.
• Embodiments of the disclosure further include methods of delivering electricity, hydrogen, or both electricity and hydrogen, produced by the cells or batteries disclosed herein to an application.
• Such applications can include, for example, cell phone towers, vehicles and fuel cells.
• the anode is aluminum
• the cathode is a catholyte in contact with a carbon foam current collector
• the catholyte is an electrolyte comprising water, sodium sulfate, sodium hydroxide, and sodium peroxydi sulfate
• the carbon current collector and anode are stacked and separated by a porous, non-conductive spacer and each stack is electrically connected by a conductor such as copper wire.
• the aluminum is oxidized per equation (A) at the anode and persulfate reduction occurs at the surface of the current collector via equation (B)
• the current collector could be characterized as a "cathode current collector,” because it distributes electrons that reduce oxidant within the electrolyte solution at the surface of the current collector (according to equation B above), wherein the electrolyte solution can be characterized as a catholyte.
• the cathode current collector can be, for example, embedded in or otherwise suitably contacting the catholyte, wherein the catholyte is the source of oxidant for reduction at the cathode current collector.
• FIG. 1 a series of three electrochemical cells are shown.
• Each cell contains an anode 100, such as aluminum in the form of a sheet or screen.
• the anode 100 is in physical contact with a porous, non-conductive spacer 110.
• the spacer is a screen that prevents physical contact between the anode and the current collector 120.
• the current collector is often a carbon foam and the spacer may be surgical tape, for example, or vinyl coated polyester.
• the stack 160 of anode 100, current collector 120 and spacer 110 may be optionally wrapped in surgical tape for physical integrity.
• Each cell is in electrical contact with an adjacent cell wherein the anode 100 and the current collector 120 of adjacent cells are in electrical contact via a conductor, such as copper wire 130.
• Electrolyte is deposited onto the cell, but the cell of FIG. 1 is not immersed in the electrolyte.
• the electrolyte may be sprayed on or delivered via atomization or compartmentalized. Often this is done so when carbon foam is the current collector, the carbon foam is saturated.
• the cell is immersed in electrolyte solution. In a wet condition, the electrolyte acts as a catholyte such that reduction occurs in the solution when a circuit is made.
• FIG. 2 represents a battery wherein the cell components of FIG. 1 in series are further connected to a Load 150 via a conductor, such as copper 140.
• a conductor such as copper 140.
• the Load 150 could be an application such as cell tower or other grid application.
• hydrogen can be collected at each anode for delivery to, for example a fuel cell or to a furnace or engine for burning hydrogen.
• Additional embodiments described below include certain membraneless electrochemical cells that contain separate first and second electrolyte solutions at the cathode and anode, respectively; batteries comprising electrochemical cells of the disclosure; methods of delivering hydrogen, electricity or both with the cells and batteries to applications; methods for boosting current in electrochemical cells of the disclosure; and various methods related to these embodiments.
• one embodiment of the disclosure includes an electrochemical cell comprising:
• first and second electrolyte solutions are in contact with each other and are immiscible, and wherein there is no membrane in between the first and second electrolyte solutions.
• each polar electrolyte solution may comprise a porous stabilizer such as borosilicate.
• the first polar electrolyte solution may be aqueous and may also comprise a base such as KOH, NaOH, Ca(OH) 2 , Li OH, RbOH, CsOH, Sr(OH) 2 , or Ba(OH) 2 .
• the pH of the first polar electrolyte solution may be, for example, between about 8 and about 14 or between about 11 and about 14.
• the oxidant may be, for example, a Vanadium ion, S 2 0 8 2" or CIO " .
• An example separating agent in this embodiment includes a salt, such as a calcium chloride or sodium sulfate.
• the electrochemical cell may be configured to operate in flow mode. It may comprise, for example, an inflow solution comprising a base (such as sodium hydroxide), an oxidant (such as S 2 0 8 2" ) and a separation agent (such as sodium sulfate). Outflow from the cell may include a base (including an aqueous solution of a base) and sodium sulfate, where the base may be sodium hydroxide.
• a base such as sodium hydroxide
• an oxidant such as S 2 0 8 2"
• a separation agent such as sodium sulfate
• a current collector may be placed within the first electrolyte solution, the second electrolyte solution, or in both.
• Example current collectors include metals as well as non- metals such as carbon foam.
• the electrochemical cell may also comprise glass wool placed in between the first and second polar electrolyte solutions.
• the second polar electrolyte solution comprises an alcohol. It may be an alcoholic solution that further comprises a base such as KOH or NaOH.
• the pH of the second polar electrolyte solution may be, for example, between about 8 and about 14 or between about 11 and about 14.
• Suitable metal ions in the second polar electrolyte include Zn 2+ and Al 3+ .
• the separation agent is a salt (such as CaCl 2 or sodium sulfate) and the alcohol in the second polar electrolyte solution is ethanol, methanol, or both.
• the second polar electrolyte comprises an alcohol and is configured to operate in flow mode with an inflow stream comprising a polar solution comprising an alcohol (such as ethanol, methanol, or both), a base (such as sodium hydroxide), a separation agent, and a metal capable of dissociating into a suitable metal ion (such as Al 3+ ).
• An outflow stream for the cell may comprise an alcohol (such as ethanol), a base (such as sodium hydroxide) and a separation salt (such as sodium sulfate).
• the electrochemical cell described here may, for example, generate hydrogen gas in the second electrolyte solution and may direct the gas to a hydrogen compressor.
• a further embodiment of the disclosure therefore includes a battery system comprising one or more of the electrochemical cells and a hydrogen compressor. Such a system may be used, for example, to power a process application such as a fuel cell.
• Another embodiment of the disclosure includes an electrochemical cell comprising:
• first and second electrolyte solutions e. borosilicate within both the first and second electrolyte solutions; wherein the first and second electrolyte solutions are in contact with each other and are immiscible, and wherein there is no membrane in between the first and second electrolyte solutions.
• the first polar electrolyte solution and second polar electrolyte solution may be of different densities, where the first electrolyte solution may comprise a halide salt (such as CaCl 2 ) and the second electrolyte solution may comprise a metal sulfate salt (such as Na 2 S0 4 ).
• the second polar electrolyte alcoholic solution may comprise, for example, ethanol or methanol.
• the pH of the first electrolyte and second electrolyte solutions can be adjusted, for example, to between about 11 to about 13 each.
• Each solution may comprise a base, such as sodium, calcium, or potassium hydroxide.
• the cathode is copper (such as a copper brush), carbon, or both and the anode is aluminum.
• the borosilicate may be, for example, Pyrex ® wool. In some embodiments, the borosilicate has a pore size of about 8 microns.
• This electrochemical cell may be configured to run in flow mode.
• An additional embodiment includes an electrochemical battery comprising one or more of the cells. When the battery comprises more than one of the electrochemical cells, the cells may be aligned, for example, in parallel geometry and arranged in a voltaic pile.
• the electrochemical cell or battery could deliver electricity to a process application, including solar farms, wind farms, household appliances, consumer goods, and toys.
• Another embodiment of the disclosure includes an electrochemical cell comprising:
• first and second electrolyte solutions are in contact with each other and are immiscible, and wherein there is no membrane in between the first and second electrolyte solutions.
• the metal solid is dispersed through the second electrolyte solution in powder form while borosilicate is placed within both the first and second electrolyte solutions.
• Example metals include zinc and aluminum.
• Metal in powder form may have, for example, an average particle size less than about 5 microns, or an average particle size between about 5 and about 30 microns.
• Non-metallic cathodes and non- metallic anodes can be made of carbon foam, for instance.
• a further embodiment includes a method of boosting current in an electrochemical cell comprising the steps of adding oxidant to the second electrolyte solution of this electrochemical cell.
• Another embodiment of the disclosure includes an electrochemical cell comprising:
• first and second electrolyte solutions are in contact with each other and are immiscible, and wherein there is no membrane in between the first and second solutions.
• the second polar electrolyte solution is an alcoholic solution such as ethanol or methanol.
• the oxidant is S 2 0 8 2" or sodium peroxydi sulfate, or both
• the metal is aluminum
• the separation agent is sodium sulfate
• the cathode and anode are carbon foam.
• a porous stabilizer (such as glass wool, borosilicate, or both) may optionally be provided in the first and second electrolyte solutions.
• the electrochemical cell may be configured to operate in flow mode.
• the cell may comprise an inflow stream that comprises an aqueous electrolyte solution and optionally also an oxidant (such as sodium peroxydi sulfate or a solution comprising peroxydi sulfate anion or both).
• an embodiment of the disclosure is a method which comprises providing additional oxidant to the electrochemical cell.
• the oxidant (such as Na 2 S 2 0 8 ) may be provided in an aqueous basic solution, for example, where the base may be NaOH.
• the oxidant may also be provided as a solid.
• the cell may further comprise an aqueous solution that outflows from the cell and that may comprise, for example, metal sulfate.
• the cell may produce between about 10 Watt-hour s/(kg of electrolyte + anode metal) and about 680 Watt-hours/(kg of electrolyte + anode metal).
• the cell may produce, for example, between about 10 Watt-hours/kg of electrolyte and about 100 Watt-hours/kg of electrolyte, and such as between about 40 Watt-hours/kg of electrolyte and about 80 Watt-hours/kg of electrolyte.
• a single electrolyte solution contains a metal solid, water, base, an oxidant, and a current collector.
• the solution is basic in some embodiments. Electrical contact is made between the current collector, such as carbon foam, and the metal solid via an external load.
• a common metal example is aluminum, such as aluminum foil, a base, such as sodium hydroxide, and the oxidant added may be sodium peroxydi sulfate, which in turn dissociates.
• the peroxydi sulfate When operating, the peroxydi sulfate reduces to sulfate. Additional sulfate, such as by the addition of a metal sulfate such as sodium sulfate, may be added. A porous stabilizer, such as glass wool or a borosilicate may be used. In such embodiments, there is only a single electrolyte solution and it may be operated in a flow mode whereby oxidant is refilled into the cell. The added oxidant may be as an aqueous solution such as with a base like sodium hydroxide or added as solid such as with granular sodium peroxydi sulfate. As sodium sulfate forms in the cell, it may optionally be removed by an apparatus for desalinization or by other mechanisms.
• Supercharging may also be achieved with two electrolyte solutions.
• oxidant such as sodium peroxydi sulfate is added to the second electrolyte solution.
• the metal in the second electrolyte solution can be aluminum and the solution is an alcoholic solution such as methanol, ethanol, or both.
• a porous stabilizer such as glass wool or a borosilicate may also be used.
• a base such as sodium hydroxide is present as is a separating agent such as sodium sulfate.
• the first electrolyte solution in such embodiments can be aqueous and is kept basic such as with NaOH.
• An oxidant such as sodium peroxydi sulfate is used and a metal sulfate such as sodium sulfate is optionally added.
• a porous stabilizer such as glass wool or a borosilicate may also be used.
• peroxydi sulfate, or another suitable oxidant is added to the second electrolyte solution and this addition causes a boost in current production.
• Such current boosts may be on the order of 50%.
• the power produced by the single-solution embodiments may be, for example, between about 10 Watt-hour s/(kg of electrolyte + anode metal) and about 680 Watt- hours/(kg of electrolyte + anode metal).
• the cell When measured per kg of electrolyte, the cell may produce, for example, between 10 and 100 Watt-hours/kg of electrolyte, including between about 40 and about 80 Watt-hours/kg electrolyte and further including between about 10 and about 60 Watt-hours/kg electrolyte.
• power densities of between about 600 and about 1000 mW/cm 2 are observed.
• the anode upon opening the circuit in a single electrolyte system, the anode becomes negatively charged and is surrounded by an ionic double layer and, for example, when considering a capacitor based on the electrochemical cell of FIG. 9, the sodium and sulfate ions make up the ionic double layer.
• the sodium concentrates next to the negatively charged surface (the stern layer) and both the sodium and sulfate ions form a diffuse layer out from the surface.
• Such a capacitor is in fact a self-charging capacitor. With respect to the cell of FIG.
• aluminum can exist in the non-negative oxidation states +3, +2, +1 and 0, but only the +3 and 0 states are energetically stable under standard battery operating conditions, with the 0 state being the solid aluminum phase.
• a strong oxidant such as S 2 0 8 2" or 2H + reacts with an aluminum atom in the 0 state, it strips 2 electrons from the solid aluminum atom (reducing itself to 2S0 4 2" ) while trying to put the aluminum atom into the energetically unstable +2 oxidation state. Because this state is energetically unfavorable, the aluminum atom sheds a third electron to put it in the stable +3 state. The third electron is conducted through the solid aluminum to the load and subsequently to the current collector, wherein the catholyte reduces another S 2 0 8 2" anion.
• Zn can exist in the non-negative oxidation states +2, +1 and 0, but only the 0 and +2 states are energetically favored.
• S 2 0 8 2" anion reacts with a zinc atom in the 0 oxidation state it strips two electrons from the zinc atom putting it in the stable +2 state, and no current is generated.
• a current can be generated.
• pairs of oxidants and reductants may be selected such that the oxidant removes sufficient electrons to create an unstable oxidation state in the reductant which may spontaneously transition to a stable oxidation state with the release of one or more additional electrons.
• the unstable oxidation state is a lower oxidation state than the stable oxidation state.
• the stable oxidation state may have an oxidation state that is +1 or +2 or more compared with the unstable oxidation state. In aluminum, for example, the stable oxidation state, +3 is one more (+1) than the unstable oxidation state.
• multiple anodes may be used with a single current collector.
• the anode is aluminum
• aluminum foil packets may be separated from each other such as with an insulator to create multiple aluminum anodes. If particulate aluminum is used, such individual particles may act as multiple anodes.
• the pH can also be used to control current.
• the pH is neutral, the S 2 0 8 2" is unable to oxidize the solid aluminum because an A1 2 0 3 film forms on the solid surface.
• the OH " anion destroys the aluminum oxide film and allows the S 2 0 8 2" anion to thereby create a current.
• the pH either with the addition of OH- ions, such as from NaOH, or by the addition of H+ ions, such as with the addition of sulfuric acid, the availability of OH- and thus control the current can be regulated.
• Lower pHs may also work, such as at around 10, provided the surface is sufficiently activated.
• electrochemical cells and batteries of the disclosure operate without the need for membranes or other devices to separate a first electrolyte solution (at the cathode) from a second electrolyte solution (at the anode).
• membranes or other devices to separate a first electrolyte solution (at the cathode) from a second electrolyte solution (at the anode).
• Electrochemical batteries of one or more cells may be prepared by combining electrochemical cells of the disclosure in parallel or in series. Examples include a voltaic pile of cells. Such cells and batteries may be used to deliver electricity to process applications such as solar farms and wind farms, hydrogen compressors, vehicles, such as electric vehicles, electrical grids, household appliances, consumer products, and toys.
• Cathodes and anodes in electrochemical cells in this disclosure may be selected from suitable materials.
• suitable cathodes include steel, carbon such as in the graphite allotrope of carbon, carbon impregnated with a metal, and carbon foam.
• Conducting carbon cloth (which is also referred to as carbon foam), for example, is a suitable cathode for many embodiments and is a conducting material.
• Suitable anodes for embodiments of the membraneless cells with multiple electrolytes include platinum, zinc, lithium, nickel, calcium, magnesium or aluminum as well as non-metallic materials such as carbon, including carbon foam.
• First and second electrolyte solutions included in embodiments of the disclosure may be polar and of different densities.
• one or more of the first polar electrolyte solution contains water and a separation agent.
• the two polar electrolyte solutions are immiscible.
• the separation agent may be used to make such fluids immiscible.
• the separation agent may be added to a mixture of an alcohol and water and at sufficient concentration it will separate the two solutions and maintain their immiscibility.
• the separation agent is often a salt.
• the solution is saturated with respect to the salt.
• salts include metal halides or ammonium salts such as sodium chloride, magnesium chloride, calcium chloride, lithium chloride and ammonium chloride.
• Other such salts include sodium sulfate, calcium sulfate, potassium sulfate, and ammonium sulfate among others.
• the same or different salts may be present in the first or second electrolyte solutions.
• sodium sulfate may be present in both.
• a salt such as sodium sulfate or sodium chloride may be present in the first electrolyte solution and ammonium chloride in the second electrolyte solution.
• calcium chloride may be present in the first electrolyte solution and sodium sulfate in the second.
• the salts are often saturated in the respective solution at or near their solubility limit.
• the first electrolyte solution is an aqueous solution and the second electrolyte solution is an alcoholic solution.
• the solution at each electrode must contain the necessary components so that oxidation-reduction will occur, thus generating electricity.
• Suitable alcohols for use in the second electrolyte solution include methanol and ethanol.
• polar solvents for use in first or second electrolyte solutions may be found in Table 1 above.
• the solvent for the particular system selected should be of sufficient dipole moment so as to dissociate the corresponding salts placed in the solvent.
• a strong acid such as sulfuric acid (e.g., 1M) may be used to make the first polar electrolyte solution acidic while the second polar electrolyte solution is neutral.
• both the first and second polar solutions are basic. These solutions may be made basic such as by the addition of a base such as LiOH, RbOH, CsOH, Sr(OH) 2 , Ba(OH) 2 , NaOH, KOH, Ca(OH) 2 , or a combination thereof.
• a base such as LiOH, RbOH, CsOH, Sr(OH) 2 , Ba(OH) 2 , NaOH, KOH, Ca(OH) 2 , or a combination thereof.
• a base such as LiOH, RbOH, CsOH, Sr(OH) 2 , Ba(OH) 2 , NaOH, KOH, Ca(OH) 2 , or a combination thereof.
• a base such as LiOH, RbOH, CsOH, Sr(OH) 2 , Ba(OH) 2 , NaOH, KOH, Ca(OH) 2 , or a combination thereof.
• an oxidant is added to the first polar electrolyte solution and a suitable metal i
• oxidants can be found in Table 2 above and examples of compounds which may dissociate into suitable metal ions in solution can be found in Table 3 above. Any metal ion oxidant pair may be chosen provided the metal oxidation by the oxidant is thermodynamically spontaneous.
• Metal ions which are commonly used in the disclosure include Al, Zn, Sn, and V.
• FIG. 3 illustrates an embodiment of an electrochemical cell that comprises first and second electrolytes.
• the electrochemical cell 10 includes a cathode 12 and an anode 14 separated by a first electrolyte solution 20 and a second electrolyte solution 22 such that the first electrolyte solution 20 is in contact with the cathode 12 and such that the second electrolyte solution 22 is in contact with the anode 14.
• the first electrolyte solution 20 and the second electrolyte solution 22 are immiscible and in contact with each other and thus can enable ion and electron exchange (e.g., H + and e-) between the anode 14 and the cathode 12.
• Each cell 10 may be electrically connected to a load 16 by a circuit 18 to enable a current flow via the circuit.
• the vertical lines connecting the electrolyte solutions and the cathode and anode electrodes in the schematic are not conduits but are merely to aid in the viewing of the schematic.
• the first electrolyte solution 20 may be a positive electrolyte or catholyte
• the second electrolyte solution 22 may be a negative electrolyte or analyte (and immiscible).
• the densities of the first electrolyte solution and the second electrolyte solution are different with the first electrolyte solution 20 being denser than the second electrolyte solution 22 such that when the cell 10 is oriented vertically with cathode 12 at the bottom, the buoyancy effect causes the second electrolyte solution 22 to layer above the first electrolyte solution 20.
• the cell 10 may optionally be configured to run in flow mode so as to support a flow battery for example.
• electrolyte solutions are provided to the cell during the operation of the battery continuously during operation.
• the first electrolyte solution 20 and the second electrolyte solution 22 may flow into the cell 10 and between the cathode 12 and the anode 14 from a first source, such as a tank, 30, or other suitable storage device, and a second source, such as a tank, 32, or other suitable storage device, respectively, as shown in FIG. 3 via conduits 21 and 25 respectively.
• the first electrolyte solution 20 and second electrolyte solution 22 may further flow out of the cell 10 via conduits 23 and 27 respectively.
• first electrolyte solution 20 and the second electrolyte solution 22 may be maintained within a laminar flow regime. In alternative embodiments, the first electrolyte solution 20 and the second electrolyte solution 22 may not flow through the cell 10 but may be replaceable.
• an electrolyte solution typically an electrolyte, often a solid, is disposed within a solvent which then becomes an electrolyte solution.
• an electrolyte when an electrolyte is disposed within a solvent where it can dissolve, the dissolution of the electrolyte solid will create ions and, if they dissociate sufficiently, the solvent becomes an electrolyte solution.
• other components are added to the solvent so that oxidation will occur at the anode and reduction at the cathode. Examples of such a component is zinc metal. When added at the anode of an operating electrochemical cell, zinc will oxidize to Zn 2+ .
• the first electrolyte solution comprises a component which dissociates into an ion selected from CIO " , Fe 3+ , V 5+ , Br 2 , and S 2 0 8 2" , which ions are reduced at the cathode.
• the second electrolyte solution comprises a component which oxidizes into an ion selected from Li + , Ca 2+ , Al 3+ , Mg 2+ , V 2+ , Zn 2+ , Si0 3 2+ , [Zn(CN) 4 ] 2" , and [Zn(OH) 4 ] 2 , which ions result from oxidation at the anode.
• the cathode, vanadium undergoes reduction from
• V 5+ to V 4+ .
• zinc is oxidized from Zn(s) to Zn 2+ .
• a methanol solvent with zinc solid on the anode side is further charged with ammonium chloride.
• the ammonium chloride dissolves and dissociates sufficiently to provide H 4 + in solution as a positively charged ion and CI " as a negatively charged ion.
• positively charged ions are provided by adding both sulfuric acid (H 2 S0 4 ) and sodium sulfate (Na 2 S0 4 ) to an aqueous V 5+ solution.
• the dissolution and dissociation into H + and Na + provides positively charged ions and S0 4 2" as a negatively charged ion on the cathode side of the electrochemical cell.
• the sodium sulfate prevents the mixing of the first and second electrolyte solutions and maintains their immiscibility.
• buoyancy forces cause the methanol solution to layer on top of the denser aqueous solution.
• This layering of immiscible fluids salt water is immiscible with methanol or ethanol
• Such embodiments may be configured for flow or for no-flow operation as described further herein.
• the zinc may be in contact with a conducting material such as conducting carbon and the cathode solution may also be in contact with such a conducting material.
• the anode is aluminum and the cathode is carbon or steel
• the first electrolyte solution contains water and CIO "
• the second electrolyte solution contains ethanol or methanol.
• each electrolyte contains a base such as NaOH, and a salt, LiCl which results in immiscible electrolyte solutions.
• the voltage supplied by such an electrochemical cell is between 1.5 and 2.1 volts.
• Such an electrochemical cell may create amperages of between about 0.1 and about 0.4 amps including about 0.2 and about 0.3 amps. Examples of components providing CIO " include Na(ClO) and Ca(C10) 2 . In such a cell, CIO " will be reduced at the cathode according to equation 1 :
• the second electrolyte may contain a component that is a metal that oxidizes, such as aluminum oxidizing to Al 3+ as per equation 2:
• Another anode choice may be magnesium which oxidizes per equation 3 :
• the anode is lithium solid and the solvent is propylene carbonate and dimethoxyethane.
• the cathode may be a suitable metal such as copper, with sodium sulfate also added.
• both the anode and cathode electrolyte solutions contain a salt.
• An example salt is a metal halide salt such as MgCl 2 .
• MgCl 2 is used in the electrolyte solutions, a voltage of 3.15 V and a current of 0.1 A/cm 2 may be achieved at 1 ohm resistance.
• amperages are recorded as A/cm 2 what is meant is amperage per areal area as opposed to specific area. For example, a 2 square centimeter piece of carbon foam has a much higher specific area than its 2 square centimeter areal area.
• the first polar aqueous electrolyte solution contains
• S 2 0 8 2" NaOH, a salt, such as a metal sulfate or metal halide salt such as CaCl 2 , and a metal cathode such as a copper, such as a copper brush, carbon foam, or a combination thereof.
• a metal sulfate salt is Na 2 S0 4.
• the S 2 0 8 2" ion originates from a salt which dissociates into that ion in, for example, the first electrolyte solution.
• the salt may be, for example, Na 2 S 2 0 8 .
• the copper may be in wire form such as a brush, for example.
• the second polar alcoholic electrolyte solution for example of a different density that the first electrolyte solution, contains an alcohol such as methanol, ethanol, or both, NaOH, a salt such as a sulfate, including metal sulfates such as Na 2 S0 4 .
• An example anode is a metal anode such as aluminum.
• the anode may be a non-metallic material such as carbon foam and a metal solid, such as in a powder form, may be dispersed within the anode solution. Examples of such metal powders, include aluminum and zinc.
• the metal powder in the solution is oxidized by the action of the electrochemical cell in a similar manner as it would oxidize if the anode itself were the metal.
• the first polar solution is aqueous and contains a separation agent such as a salt like CaCl 2 or Na 2 S0 4 .
• the cathode in contact with the first electrolyte solution in such embodiments may be a metal like copper or a non-metal like carbon foam.
• a stabilizer such as glass wool or a borosilicate such as Pyrex® may be used.
• the oxidant in such solutions is often S 2 0 8 2" which may be sourced from Na 2 S 2 0 8 , for example.
• the second polar solution is often an alcohol such as ethanol or methanol.
• the anode in contact with the second electrolyte solutions in such embodiments is often aluminum or carbon foam.
• Separation agents such as Na 2 S0 4 are often deployed at or near saturation concentrations in the first polar electrolyte solution, the second polar electrolyte solution, or both.
• Suitable metal ions are often Aluminum such as Al 3+ which may be sourced, for example from Aluminum foil or Aluminum powder. Zn 2+ may also be used, for example, in such embodiments.
• Both the first and second polar electrolyte solutions can be rendered basic by a base such as NaOH where the pH is greater than and often between 11 and 14.
• hydrogen gas is generated in the second polar electrolyte solution. Such gas may be vented and delivered to a process application like a fuel cell. The hydrogen can be fed to a hydrogen compressor prior to delivery, for example. Electricity generated from one or more cells may be used to power the hydrogen compressor.
• the electrochemical cell may be run in a flow mode in such operations where electrolyte solution is replenished and spent solution removed.
• the inflow solution may be an aqueous solution comprising a base, an oxidizing agent, and a separation agent for the first polar electrolyte solution and comprising an alcohol, a metal capable of dissociating into a suitable metal ion, a base and a separation agent.
• the outflow solutions comprise an aqueous solution of base and separation agent for the first electrolyte solution and alcohol, base, and separation agent for the second polar electrolyte solution.
• the outflow may also contain AI2O3.
• the pH of each solution is made basic by the use of NaOH, KOH, Ca(OH) 2 , or another base. With such a base, the pH may be adjusted to between about 8 and about 14, between about 9 and about 14, between about 10 and about 14, between about 11 and about 14, between about 12 and about 14, between about 11 and about 13 and all values between about 8 and about 14 including about 8, 9, 10, 11, 12, 13, and 14.
• the electrochemical cells may further contain a porous stabilizer.
• the porous stabilizer allows for the passage of fluid and also can be placed across the first and second electrolyte solutions and help maintain the separation between the solutions including during turbulent movement.
• a porous stabilizer may be any porous media, Examples of porous stabilizers are glass wool and borosilicates including Pyrex®.
• the porous stabilization may be used in each of the first and second electrolyte solutions and it enables the electrochemical cell containing the two electrolyte solutions to spin, bounce or rotate rapidly with little fluid displacement. Examples of borosilicate include such borosilicate with a pore size of about 8 ⁇ . Pyrex ® wool is one such borosilicate.
• Such electrochemical cells may be run in a flow or non-flow mode.
• Such electrochemical cells can have superior current density and voltages than cells of the prior art.
• electrochemical cells of these embodiments have been measured for 18 hours at 1 ohm resistance with starting voltages and amperages of about 2.07 V and 0.16 A/cm 2 and concluding at about 1.55 V and 0.088 A/cm 2 .
• porous stabilizers affects some or all of the following characteristics of batteries and electrochemical cells of the disclosure: wettability boundary conditions; no slip and slip boundary conditions; conductivity, including resistivity and friction; dispersivity or mixing between adjacent fluids; porosity (e.g., relative volume for flow); tortuosity (e.g., length and complexity of trajectories); connectivity (e.g., species and electrical); particle size distribution (e.g., packing); relative conductivity (e.g., multiphase resistivity); multiscale (e.g., discrete scale separation); surface absorptivity (e.g., double layer capacitance); surface reactivity (e.g., pseudo capacitance); diagenesis (e.g., dissolution or deposition); and swelling (e.g., interfacial forces).
• the porous media may include nanostructures or nanoparticles. Such porous media may be used, for example, at the cathode or anode. Further examples of such porous media include
• Separators or interconnects may be used to separate adjacent cells to prevent short circuiting such batteries but still provide for electrical communication.
• Stabilizers may also be used in between the first and second electrolyte solutions of an electrochemical cell.
• the anode is non-metallic, such as carbon foam, and a metal, such as aluminum or zinc, is added as a solid to the anode solution, it is often in the form of a powder and a common particle size is one where the average size is less than 5 microns. In other embodiments, the average size is between about 5 microns and 30 microns.
• the powder is dispersed throughout the solution so that the solution appears cloudy. Such a dispersion is useful for the performance of the cell. Generally, the smaller the particle, the longer it takes for the particles to settle out from the dispersion in accordance with Stokes' law. Thus, from a suspension stability stand point, smaller particles are favored.
• the half-cell reaction for some such embodiments is:
• Zn(s) ⁇ Zn 2+ + 2e ⁇ EQ. 7 is the half-cell reaction at the anode the anode itself is zinc, or is suspended in the anode solution as a solid.
• hydrogen gas may be liberated by the chemical reactions within the electrochemical cell under basic conditions.
• hydrogen may be created without the liberation of C0 2 or CO.
• the resulting hydrogen may be collected for storage or redistribution or routed to a second electrochemical cell with a platinum membrane for additional energy generation.
• the suitable metal ion is Al 3+ and the second polar electrolyte solution contains a polar solvent such as a methanol, ethanol or both
• hydrogen gas may be liberated as a result of subsequent reactions in such electrochemical cells.
• a suitable oxidant herein is S2O8 2" .
• the rate at which hydrogen gas is generated is a function of the distance between the copper/carbon and metal, such as aluminum, in the second polar electrolyte solution, for example, aluminum.
• the greater the distance the lower the rate hydrogen gas is released and the lower the current.
• surface area affects the rate in that the greater the surface area, generally the greater the rate of hydrogen produced. Hydrogen may be produced in a flow or non-flow mode.
• the metal anode is oxidizable by the oxidant and the oxidant is reduced at the cathode.
• a suitable metal ion is present in the anode side along with a base such as NaOH in a polar solution comprising for example, methanol or ethanol.
• Suitable metals are those which produce hydrogen when placed in contact with a base in the second polar electrolyte solution.
• Such metals have a metal-metal ion redox potential that is negative.
• examples of such fluids include alcohols such as methanol, ethanol, propyl alcohol, or isopropyl alcohol.
• Water is another such fluid such as in a mixture with an alcohol, however, in the presence of a separating salt, water tends to collect on the cathode side of an electrochemical cell of the disclosure.
• the amount of hydrogen that is created from a battery may be up to about 100kg of hydrogen per day including between about 10 kg and 100 kg and all values in between. Hydrogen gas may be collected for use in such electrochemical cells.
• a single electrochemical cell with 3cm 2 Al metal placed in the second polar electrolyte solution was measured in an electrochemical cell set up generally in accordance with Fig. 8 to produce about 0.5 kg of the H 2 per hour. A larger surface area metal placed in the second polar electrolyte solution will produce more hydrogen.
• Metals placed in the second polar electrolyte solution to produce suitable metal ions may be provided as sheets such as Aluminum sheets, folded over or serpentine in shape may also be provided.
• Other forms of Aluminum solid include powders such as in a slurry, or nano structures.
• the hydrogen may be stored for future use, such as under compressed conditions. Examples of uses of hydrogen includes fuel cells. Such fuel cells may be used to power vehicles, for instance.
• the current may be boosted or "super charged" by the addition of oxidant to the second polar electrolyte solution.
• oxidant for example, in electrochemical cells where aluminum is disposed with an alcohol or aqueous solution, sodium peroxydi sulfate may be added to the alcohol solution to boost the current observed from the electrochemical cell.
• a second polar electrolyte solution is not needed to create such boosted current.
• it may be useful to stack more than one electrochemical cell. The stacking of cells may be enabled, for example, by the use of three or more immiscible fluids having three or more different densities.
• a second cathode opposite the first cathode at a second distance from the anode is provided and a third electrolyte solution in contact with the second cathode and the second electrolyte solution is further provided wherein the third and second electrolyte solutions are in contact with each other and are immiscible, and wherein there is no membrane in between the third and second electrolyte solutions.
• the third electrolyte solution may be polar and will be a greater density than the first two electrolyte solutions.
• An example of a third electrolyte solution that is denser than water is one that contains propylene carbonate as a solvent.
• the third electrolyte solution may contain a salt and may be saturated with respect to that salt. Batteries with such cells may be configured in flow or no flow mode.
• a battery may include a cell 11 including a first electrolyte solution 20, a second electrolyte solution 22, and a third electrolyte solution 24.
• the cell 11 includes one cathode 12 operating with two anodes 14 to generate electricity supplied to the load 16 via circuit 18.
• the third electrolyte solution 24 is denser than the first electrolyte solution 20 and the second electrolyte solution 22.
• the third electrolyte solution 24 is immiscible relative to the first electrolyte solution 20 and/or the second electrolyte solution 22.
• the second electrolyte solution 20 is disposed in a layer above the first electrolyte solution 22, and the first electrolyte solution 22 is disposed in a separate layer above the third electrolyte solution 24.
• Optional tanks 30 and 32 acting as sources for electrolyte solutions, and pumps 50 and 52 (or by capillarity, reverse osmosis, a ratchet, swelling pressure, or gravity), may be used to deliver electrolyte solutions to the cell in flow mode, for example via conduits 21 and 25 respectively.
• the first electrolyte solution 20 and second electrolyte solution 22 may further flow out of the cell 11 via conduits 23 and 27 respectively. They may be directed to waste or to other tanks. In some embodiments, flow could be reversed from said other tanks to recharge cell 11.
• the cell can be arranged with a cathode on top and bottom and an anode in the middle.
• the third electrolyte solution 24 may be supplied to the cell 11 from a third source 34 via conduit 31 with pump 54 (or by capillarity, reverse osmosis, a ratchet, swelling pressure, or gravity) which may be used in flow mode.
• the third electrolyte solution 24 may further flow out of cell 11 via conduit 33. This may be directed to waste or to another tank. In some embodiments, flow could be reversed from said another tank to recharge cell 11.
• the third electrolyte solution 24 may be directed to waste or to other tanks. In some embodiments, flow could be reversed and from the other tanks to recharge the cells.
• the third electrolyte solution 24 may not flow through the cell 11 but may be replaceable.
• the vertical lines connecting the electrolyte solutions and the cathode and anode electrodes in the schematic are not conduits but are merely to aid in the viewing of the schematic.
• electrochemical cell 11a is a three-layer system presented with two cathodes 12 and one anode 14.
• First electrolyte solution 20 is in contact with cathode 12 and second electrolyte solution 22 which in turn is in contact with anode 14 and third electrolyte solution 24.
• Cathode 12 is in contact with the third electrolyte solution 24 and load 16 via circuit 18.
• An optional reductant (such as H 2 gas) 26 may supply the H 2 to anode 14 via conduit 31a.
• Flow tanks, conduits, and pumps (or by capillarity, reverse osmosis, a ratchet, swelling pressure, or gravity) may be used to run electrochemical cell 1 la in flow mode and thus allow for recharging.
• a first and second electrolyte solution are of different densities and immiscible due to the presence of a salt in the first electrolyte solution and are in contact without a membrane.
• the cell is configured to run in a no flow mode. Batteries may be made of such cells such as in parallel or series geometry and/or a voltaic pile. The electricity from such batteries may be delivered to a process application such as solar farms, wind farms, household appliances, consumer goods, or toys.
• Al Anode A strip of aluminum screen which is 200 mm by 25 mm is cut and the screen is folded in half lengthwise three times, resulting in a 25 mm by 25 mm square 8 layers thick.
• Carbon foam current collector A strip of carbon felt which is 100 mm by
• Copper wire A length of bare copper wire is cut which is aboutlOO mm long.
• a sandwich of the aluminum from a first unit, the spacer, and the carbon foam from a second unit is made.
• This sandwich is then wrapped in one layer of 3M surgical tape, which ensures that there is light compression of the sandwich construct so that the gap between the aluminum and carbon is the thickness of the spacer.
• the surgical tape also works as a sponge to absorb the electrolyte when so exposed to ensure adequate saturation of the battery.
• This sandwich may be referred to as a stack.
• the assembly can be repeated for as many units as desired to create electrochemical cells in series.
• the ends of the cells can be connected via a common load to create an electrochemical battery.
• electricity or hydrogen or both may be generated and may be delivered to an application.
• Example 3 Al/peroxydisulfate electrochemical cell/battery with immiscible electrolyte solutions without a membrane
• the figure represents both an electrochemical cell and a battery with a battery being defined as containing one or more electrochemical cells.
• the cel ⁇ attery was made in a glass beaker.
• Aluminum solid was used as anode 62 and electrically connected via circuit 18 and Load 16 to cathode 63, conducting carbon cloth or copper depending on the specific experiment.
• the anode was placed in an electrolyte solution 22c containing ethanol or methanol (multiple were tested), which was loaded with sodium sulfate and sodium hydroxide.
• the cathode was placed in contact with an electrolyte solution 20c and loaded with sodium hydroxide, calcium chloride, and Na 2 S 2 0 8 . Although each solution is polar, the different electrolyte solutions are immiscible.
• the anode electrode is aluminum.
• Pyrex ® wool is loaded into the beaker in between the cathode and anode.
• the Pyrex ® wool forms a porous medium in which fluids are imbedded.
• Other porous media materials such as other borosilicates, may be used.
• the concentrations of sodium and calcium salts were such that they were near or at their solubility limit for the system.
• the cell/battery of FIG. 5 could be run in flow mode by attaching optional tanks 30 and 32 and pumps 50 and 52 (or by capillarity, reverse osmosis, a ratchet, swelling pressure, or gravity) via conduits 21 and 25 respectively.
• the outflow from the cell/battery 23 and 27 could be routed to waste or to an external tank for recharge purposes via reversing polarity.
• the rate of addition of a fluid to increase or decrease the thickness of a layer can be used to change the pressure in the layer.
• the anode oxidation reaction rate such as Al(s) ⁇ A1 3+ , can be controlled by adjusting the two pressures in electrolyte solutions (by adjusting the rate which controls the thickness of the two solutions) which in turn changes the proximity of
• Example 4 Zn/peroxydisulfate electrochemical cell/battery with immiscible electrolyte solutions without a membrane
• a no flow electrochemical cell/battery configured in accordance with the schematic of FIG. 6 (other than the flow portion of the schematic) was prepared.
• the figure represents both an electrochemical cell and a battery with a battery being defined as containing one or more electrochemical cells.
• the cel ⁇ attery was made in a glass beaker. Carbon foam was used as an anode-electrode 62a and electrically connected via circuit 18 and Load 16 to cathode 63a, which was also carbon foam.
• the anode was placed in an electrolyte solution 22d containing ethanol or methanol depending on the experiment (multiple runs were performed), which was loaded with zinc powder, sodium sulfate and sodium hydroxide.
• the cathode was placed in contact with an electrolyte solution 20c in water and loaded with sodium hydroxide, calcium chloride, and Na 2 S 2 0 8 . Although each solution is polar, the different electrolyte solutions are immiscible. Further, they have different densities with the peroxydi sulfate solution being denser, and thus on the bottom and the less dense neutral alcohol (ethanol or methanol) solution on top.
• Pyrex ® wool was loaded into the beaker in between the cathode and anode. The Pyrex ® wool forms a porous medium in which fluids are imbedded. Other porous media materials, such as other borosilicates, may be used.
• the concentrations of sodium and calcium salts were such that they were near or at their solubility limit for the system.
• the cell/battery of FIG. 6 could be run in flow mode by attaching optional tanks 30 and 32 and pumps 50 and 52 (or by capillarity, reverse osmosis, a ratchet, swelling pressure, or gravity) via conduits 21 and 25 respectively.
• the outflow from the cell/battery 23 and 27 could be routed to waste or to an external tank for recharge purposes via reversing polarity.
• voltages of between 1.75 V and 1.89 V were recorded and a current of .12 A/cm 2 were recorded at one ohm in ethanol and about 1.52V at 0.12 A/cm 2 in methanol.
• the rate of addition of a fluid to increase or decrease the thickness of a layer can be used to change the pressure in the layer.
• the anode oxidation reaction rate such as Zn(s) ⁇ Zn 2+ , can be controlled by adjusting the two pressures in electrolyte solutions (by adjusting the rate which controls the thickness of the two solutions) which in turn changes the proximity of the zinc to the ions in the cathode
• reaction such as, for example, the S 2 0 8 ion.
• the reaction may also be reversible so that the cell or a battery with multiple cells may be recharged.
• Example 5 Additional embodiment of Al/peroxydisulfate electrochemical cell/battery with immiscible electrolyte solutions without a membrane
• a no flow electrochemical cell/battery configured in accordance with the schematic of FIG. 7 (other than the flow portion of the schematic) was prepared.
• the figure represents both an electrochemical cell and a battery with a battery being defined as containing one or more electrochemical cells.
• the cel ⁇ attery was made in a glass beaker. Carbon foam was used as an anode-electrode 62a and electrically connected via circuit 18 and Load 16 to cathode 63a, which was also carbon foam.
• the anode was placed in an electrolyte solution 22e containing ethanol or methanol depending on the experiment (multiple runs were performed), which was loaded with aluminum powder, sodium sulfate and sodium hydroxide.
• the cathode was placed in contact with an electrolyte water solution 20c and loaded with sodium hydroxide, calcium chloride, and Na 2 S 2 0 8 .
• each solution is polar, the different electrolyte solutions are immiscible. Further, they have different densities with the peroxydi sulfate solution being denser, and thus on the bottom and the less dense neutral alcohol (ethanol or methanol) solution on top.
• Pyrex ® wool is loaded into the beaker in between the cathode and anode. The Pyrex ® wool forms a porous medium in which fluids are imbedded. Other porous media materials, such as other borosilicates, may be used.
• the concentrations of sodium and calcium salts were such that they were near or at their solubility limit for the system.
• the cell/battery of FIG. 7 could be run in flow mode by attaching optional tanks 30 and 32 and pumps 50 and 52 (or by capillarity, reverse osmosis, a ratchet, swelling pressure, or gravity) via conduits 21 and 25 respectively.
• the outflow from the cell/battery 23 and 27 could be routed to waste or to an external tank for recharge purposes via reversing polarity. After running for three hours, a voltage of 1.9 V was recorded and a current of 0.14 A/cm 2 .
• the rate of addition of a fluid to increase or decrease the thickness of a layer can be used to change the pressure in the layer.
• the anode oxidation reaction rate such as Al(s) ⁇ A1 3+ , can be controlled by adjusting the two pressures in electrolyte solutions (by adjusting the rate which controls the thickness of the two solutions) which in turn changes the proximity of the aluminum to the ions in the cathode
• FIG. 8 is a schematic of an electrochemical cell in flow mode.
• Flow batteries have the advantage that they are instantly rechargeable via continual replacement of the electrolytes.
• flow batteries are like fuel cells, but rather than using hydrogen and oxygen, they employ liquid electrolytes.
• the metal that is often on the anode side of redox flow-batteries is in the form of a very fine powder that is premixed with the analyte to form a colloidal suspension and pumped through a porous carbon current collector where oxidation takes place. On the cathode side a strong oxidant is dissolved in the catholyte for the reduction step.
• Example single cell amperages range from 0.25A/cm 2 to 0.1A/cm 2 with voltages ranging from 1.5V to 3.25V.
• a first electrolyte solution is made by loading water with NaOH, Na 2 S0 4 and Na 2 S 2 0 8 . Inflow and outflow ports are provided so that electrolyte solution can be replenished and removed for flow purposes.
• the first electrolyte solution uses a carbon foam current collector and is stabilized with glass wool.
• Inflowing solution contains water, NaOH, Na 2 S0 4 , and Na 2 S 2 0 8 whereas outflow is water, NaOH, and Na 2 S0 4 .
• a material, often made of plastic, with holes may be used to separate the first electrolyte solution from the second and may contain glass wool.
• a second electrolyte is made by adding NaOH, Al powder and Na 2 S0 4 to ethanol.
• the Na 2 S0 4 is added at a sufficiently high concentration to keep separate the aqueous first electrolyte solution from the ethanolic second electrolyte solution.
• Inflows and outflows are provided for the second electrolyte solution with an inflow being an ethanolic solution of NaOH and Na 2 S0 4 with added Al in powder form.
• the outflow contains ethanol, sodium hydroxide, Al 2 0 3 ,Na 2 S0 4 , and NaAl(OH) 4 .
• the current collector is carbon foam which is in electrical contact via a load with the current collector of the first electrolyte solution. Glass wool stabilizes the second electrolyte solution.
• hydrogen gas is formed in the second electrolyte solution and may be removed as set forth in FIG. 8 to, for example, a hydrogen compressor, for hydrogen delivery to a process application such as a fuel cell.
• the electricity generated by the electrochemical cell may be used to power the hydrogen compressor.
• a 900 cm 2 Aluminum sheet placed in the second electrolyte solution should provide current of at least 0.1 A/cm 2 resulting in 90A of current, at 1 ohm and 2 volts, this provides 180 watts of power.
• 6 electrochemical cells in series would be more than sufficient to run a typical hydrogen compressor.
• Example 7 Electrochemical Cell with Single Solution which may be used as a capacitor
• FIG. 9 An electrochemical cell was prepared in accordance with FIG. 9 in a no- flow mode. The cell could be run in flow mode, however, and FIG. 9 illustrates how that could be done.
• An electrolyte solution was made from 10 grams of sodium peroxydi sulfate, 10 grams of sodium hydroxide, 10 grams of sodium sulfate and 200 mis of water.
• 1.5 grams of Al foil was compressed into a 1x2x1 cm block and connected via copper wire to a meter in the cell and 20 mis of the electrolyte solution was added to the cell.
• a carbon foam current collector was also connected to the meter in the cell.
• Electrochemical cell 20d therefore, is similar to 20c, except for the addition of sodium sulfate.
• concentrated (2M) sodium peroxydi sulfate and NaOH (pH15) was added dropwise to the cell near the Al foil.
• Spikes in power may be obtained by adding oxidant, such as with the addition of sodium peroxydi sulfate and sodium hydroxide followed by opening the electrochemical circuit such as by disconnecting the lead. The disconnection may be used to build a capacitor. The capacitor charge may then be discharged by reconnecting the lead and closing the circuit. It is believed that reduction-oxidation capacitance is charged chemically by continuous oxidation of the aluminum while the circuit is open creating a net negative charge on the aluminum, which in turn induces a double ionic layer (sodium and sulfate) to form next to the aluminum surface with cations favored toward the surface.
• oxidant such as with the addition of sodium peroxydi sulfate and sodium hydroxide
• This cycle, of opening and closing the circuit may be repeated at the same time that bulk electrolyte and solid aluminum is passed through the system. Alternatively, the resulting sodium sulfate, aluminum oxide and sodium aluminate may be removed.
• electrochemical cells are stacked vertically. In alternative embodiments, adjacent electrochemical cells, for example, may be disposed in other orientations to make batteries. [00152]
• a variety of embodiments according to the present disclosure are contemplated. Such embodiments may be employed in a variety of methods, processes, procedures, steps, and operations as a means of providing electrochemical cells and batteries. While the disclosure has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character, it being understood that only certain exemplary embodiments have been shown and described. Those skilled in the art will appreciate that many modifications are possible in the example embodiments without materially departing from this disclosure. Accordingly, all such modifications are intended to be included within the scope of this disclosure as defined in the following claims. Indeed, this disclosure is not intended to be exhaustive or to limit the scope of the disclosure.
• An electrochemical cell comprising:
• Clause 2 The electrochemical cell of Clause 1, further comprising a single electrolyte solution.
• Clause 3 The electrochemical cell of Clause 2, wherein the cell is saturated with electrolyte.
• Clause 4 The electrochemical cell of Clause 3, wherein the cell is not immersed in an electrolyte bath.
• Clause 5 The electrochemical cell of Clause 1, wherein the cell is wrapped in a microporous material.
• Clause 6 The electrochemical cell of Clause 1, wherein the anode is selected from aluminum, gallium, indium, thallium and alloys comprising at least one of these.
• Clause 7 The electrochemical cell of Clause 6, wherein the anode is aluminum.
• Clause 8 The electrochemical cell of Clause 1, wherein the current collector is selected from steel, the graphite allotrope of carbon, carbon impregnated with a metal and carbon foam.
• Clause 10 The electrochemical cell of Clause 1, wherein the porous, non- conductive spacer is selected from an organic polymer, surgical tape, fiberglass film, glass wool, wood, paper, cloth, cardboard and nylon.
• Clause 11 The electrochemical cell of Clause 10, wherein the spacer is vinyl coated polyester.
• Clause 12 The electrochemical cell of Clause 2, wherein the electrolyte comprises water and one or more salts.
• Clause 13 The electrochemical cell of Clause 12, wherein at least one salt is an oxidant.
• Clause 14 The electrochemical cell of Clause 12, wherein the electrolyte comprises two salts.
• Clause 15 The electrochemical cell of Clause 14, wherein the electrolyte comprises a salt of peroxydi sulfate and a salt of sulfate and further comprises a base.
• peroxydi sulfate salt is sodium peroxydi sulfate and the sulfate salt is sodium sulfate and the base is sodium hydroxide.
• Clause 17 The electrochemical cell of Clause 2, wherein the electrolyte comprises one of water or an alcohol.
• Clause 18 The electrochemical cell of Clause 17, wherein the electrolyte is a catholyte.
• Clause 19 The electrochemical cell of Clause 17, further comprising an oxidant.
• Clause 20 The electrochemical cell of Clause 19, further comprising a metal salt.
• Clause 21 The electrochemical cell of Clause 20, wherein the oxidant and metal salt have different anion components.
• Clause 22 The electrochemical cell of Clause 21, wherein the oxidant is sodium peroxydi sulfate and the metal salt is sodium sulfate.
• Clause 23 The electrochemical cell of Clause 17, further comprising a base.
• Clause 24 The electrochemical cell of Clause 23, wherein the base is NaOH.
• Clause 25 An electrochemical cell of any one of Clauses 1-24, wherein the cell is electrically connected to a load.
• Clause 26 An electrochemical battery comprising one or more
• Clause 27 A method which comprises producing electricity or hydrogen with an electrochemical cell of Clause 25 and delivering the electricity to an application.
• Clause 28 A method which comprises producing electricity or hydrogen with an electrochemical battery of Clause 26 and delivering the electricity or hydrogen to an application.
• a method of making an electrochemical cell which comprises:
• Clause 30 The method of Clause 29, which comprises contacting the cell with the single electrolyte solution by spraying the electrolyte solution onto the cell.
• Clause 31 The method of Clause 29, which comprises contacting the cell with droplets of the single electrolyte solution via drip.
• Clause 32 The method of Clause 29, which comprises contacting the cell with an atomized mist of the single electrolyte solution.
• a method of operating an electrochemical cell which comprises:
• Clause 34 The method of Clause 33, which further comprises:
• Clause 35 The method of Clause 34, which comprises 4) withdrawing spent electrolyte solution, or one or more components thereof, simultaneously with 3) providing additional electrolyte solution, or one or more components thereof.
• Clause 36 The method of any one of Clauses 33-35, wherein the single electrolyte solution comprises one or more of the following components: solvent, oxidant, metal salt, and base.
• Clause 38 The method of Clause 37, further comprising the step of reconnecting the load.
• Clause 40 The electrochemical cell of any one of Clauses 1-4, wherein the cell is wrapped in a microporous material.
• Clause 41 The electrochemical cell of any one of Clauses 1-4 and 40, wherein the anode is selected from aluminum, gallium, indium, thallium and alloys comprising at least one of these.
• Clause 42 The electrochemical cell of Clause 41, wherein the anode is aluminum.
• Clause 43 The electrochemical cell of Clause 42, wherein the aluminum is in the form of a screen.
• Clause 44 The electrochemical cell of Clause 43, wherein the aluminum thickness in the screen is between about 0.1 mm and about 0.3 mm.
• Clause 45 The electrochemical cell of any one of Clauses 1-4 and 40-44, wherein the current collector is carbon foam.
• Clause 46 The electrochemical cell of any one of Clauses 1-4 and 40-45, wherein the porous, non-conductive spacer is selected from an organic polymer, surgical tape, fiberglass film, glass wool, wood, paper, cloth, cardboard and nylon.
• Clause 47 The electrochemical cell of Clause 46, wherein the spacer is vinyl coated polyester.
• Clause 48 The electrochemical cell of Clause 46, wherein the spacer is a screen.
• Clause 49 The electrochemical cell of Clause 48, wherein the spacer thickness in the screen is between about 0.1 mm and about 0.8 mm and the spacer is vinyl coated polyester.
• Clause 50 The electrochemical cell of Clause 1, further comprising a metal conductor between the anode and an adjacent current collector from a second electrochemical cell and wherein the electrochemical cell of Clause 1 is configured to operate as a flow cell.
• Clause 51 The electrochemical cell of Clause 50, wherein the metal conductor is copper wire.
• Clause 52 The electrochemical cell of any one of Clauses 40-51, wherein the microporous material is surgical tape.
• Clause 53 The electrochemical cell of any one of Clauses 2-4 and 40-52, wherein the electrolyte comprises water and one or more salts, wherein at least one of the salts is an oxidant.
• Clause 54 The electrochemical cell of Clause 53, wherein the electrolyte comprises two salts.
• Clause 55 The electrochemical cell of Clause 54, wherein the electrolyte comprises a salt of peroxydi sulfate and a salt of sulfate and further comprises a base.
• Clause 56 The electrochemical cell of Clause 55, wherein the
• peroxydi sulfate salt is sodium peroxydi sulfate and the sulfate salt is sodium sulfate and the base is sodium hydroxide.
• An electrochemical battery comprising one or more
• Clause 58 The electrochemical battery of Clause 57, comprising two or more electrochemical cells arranged in series.
• Clause 59 The electrochemical battery of Clause 57, comprising two or more electrochemical cells arranged in parallel.
• Clause 60 The electrochemical battery of Clause 57, comprising electrochemical cells arranged in series and in parallel.
• Clause 61 The electrochemical battery of any one of Clauses 57-60, further comprising an electrolyte wherein the electrolyte comprises water and one or more salts, wherein at least one of the salts is an oxidant.
• Clause 62 The electrochemical battery of Clause 61, wherein the electrolyte comprises two salts.
• Clause 63 The electrochemical battery of Clause 62, wherein the electrolyte comprises a salt of peroxydi sulfate and a salt of sulfate and further comprises a base and wherein the electrochemical battery is configured as a flow battery.
• Clause 64 The electrochemical battery of Clause 63, wherein the peroxydi sulfate salt is sodium peroxydi sulfate and the sulfate salt is sodium sulfate and the base is sodium hydroxide.
• Clause 65 The electrochemical battery of any one of Clauses 57-64, which produces electricity.
• Clause 66 The electrochemical battery of any one of Clauses 57-64, which produces hydrogen.
• Clause 67 The electrochemical battery of any one of Clauses 57-64, which produces electricity and hydrogen.
• Clause 68 A method which comprises delivering electricity produced by the electrochemical battery of Clause 65 to an application.
• Clause 69 A method which comprises delivering hydrogen produced by the electrochemical battery of Clause 66 to an application.
• Clause 70 The method of Clause 68, wherein the application is a cell phone tower or a vehicle.
• Clause 71 The method of Clause 69, wherein the application is a fuel cell or a vehicle.
• Clause 72 The electrochemical cell of any one of Clauses 2-4 and 40-56, wherein the electrolyte comprises one of water or an alcohol.
• Clause 73 The electrochemical cell of Clause 72, wherein the electrolyte is a catholyte.
• Clause 74 The electrochemical cell of Clause 72 or 73, further comprising an oxidant.
• Clause 75 The electrochemical cell of Clause 74, further comprising a metal salt.
• Clause 76 The electrochemical cell of Clause 75, wherein the oxidant and metal salt have different anion components.
• Clause 77 The electrochemical cell of Clause 76, wherein the oxidant is sodium peroxydi sulfate and the metal salt is sodium sulfate.
• Clause 78 The electrochemical cell of any one of Clauses 72-77, further comprising a base.
• Clause 79 The electrochemical cell of Clause 78, wherein the base is NaOH.
• Clause 80 The electrochemical battery of any one of Clauses 57-60, further comprising an electrolyte wherein the electrolyte comprises one of water or an alcohol.
• Clause 81 The electrochemical battery of Clause 80, wherein the electrolyte is a catholyte.
• Clause 82 The electrochemical battery of Clause 80 or 81, further comprising an oxidant.
• Clause 83 The electrochemical battery of Clause 82, further comprising a metal salt.
• Clause 84 The electrochemical battery of Clause 83, wherein the oxidant and metal salt have different anion components.
• Clause 85 The electrochemical battery of Clause 84, wherein the oxidant is sodium peroxydi sulfate and the metal salt is sodium sulfate.
• Clause 86 The electrochemical battery of any one of Clauses 80-85 further comprising a base.
• Clause 87 The electrochemical battery of Clause 86, wherein the base is NaOH.
• An electrochemical cell comprising:
• Clause 89 The electrochemical cell of Clause 88, wherein the cell is wrapped in a microporous material.
• Clause 90 The electrochemical cell of Clause 88 or Clause 89, wherein the anode is selected from aluminum, gallium, indium, thallium and alloys comprising at least one of these.
• Clause 91 The electrochemical cell of Clause 90, wherein the anode is aluminum.
• Clause 92 The electrochemical cell of Clause 90 or Clause 91, wherein the anode is in the form of a screen.
• Clause 93 The electrochemical cell of Clause 92, wherein the anode thickness in the screen is between about 0.1 mm and about 0.3 mm.
• Clause 94 The electrochemical cell of any one of Clauses 88-93, wherein the current collector is selected from steel, the graphite allotrope of carbon, carbon impregnated with a metal and carbon foam.
• Clause 95 The electrochemical cell of Clause 94, wherein the current collector is carbon foam.
• Clause 96 The electrochemical cell of any one of Clauses 88-95, wherein the porous, non-conductive spacer is selected from an organic polymer, surgical tape, fiberglass film, glass wool, wood, paper, cloth, cardboard and nylon.
• Clause 97 The electrochemical cell of Clause 96, wherein the spacer is vinyl coated polyester.
• Clause 98 The electrochemical cell of any one of Clauses 88-97, wherein the spacer is a screen.
• Clause 99 The electrochemical cell of Clause 98, wherein the spacer thickness in the screen is between about 0.1 mm and about 0.8 mm and the spacer is vinyl coated polyester.
• electrochemical cell comprises a single electrolyte solution and is electrically connected to a load, and wherein the cell produces between about 10 Watt-hour s/(kg of electrolyte + anode metal) and about 680 Watt-hours/(kg of electrolyte + anode metal).
• electrochemical cell comprises a single electrolyte solution and is electrically connected to a load, and wherein the cell produces between about 10 Watt-hours/kg of electrolyte and about 100 Watt-hours/kg of electrolyte.
• An electrochemical cell comprising a single aqueous electrolyte solution in contact with a non-metallic current collector, an oxidant, and a metal solid wherein current travels from the metal solid to the current collector via a load.
• Clause 103 The electrochemical cell of Clause 102, wherein the aqueous electrolyte solution is basic and the oxidant is 8 2 0 8 2" .
• Clause 104 The electrochemical cell of Clause 102, wherein the aqueous electrolyte solution further comprises sodium hydroxide.
• Clause 105 The electrochemical cell of any one of Clauses 102- 104, wherein the metal solid is selected from aluminum, gallium, indium, thallium and alloys comprising at least one of these.
• Clause 106 The electrochemical cell of Clause 105, wherein the method solid is aluminum in foil form.
• Clause 107 The electrochemical cell of any one of Clauses 102-106, further comprising a porous stabilizer.
• Clause 108 The electrochemical cell of any one of Clauses 102-107, further comprising a metal sulfate and wherein the current collector is carbon foam and the porous stabilizer is glass wool or a borosilicate or both.
• Clause 109 The electrochemical cell of Clause 108, wherein the metal sulfate is Na 2 SC>4.
• Clause 110 The electrochemical cell of any one of Clauses 102-109 wherein the pH is greater than 12.
• Clause 111 The electrochemical cell of Clause 110, wherein the pH is greater than 13.
• Clause 112. The electrochemical cell of Clause 111, wherein the pH is greater than 14.
• Clause 113 The electrochemical cell of any one of Clauses 102-112, wherein between about 10 Watt-hours/kg of electrolyte and about 100 Watt-hours/kg of electrolyte is produced.
• Clause 114 The electrochemical cell of Clause 113, wherein the power produced per square centimeter of metal solid is between about 600 mW and about 1000 mW.
• Clause 115 The electrochemical cell of any one of Clauses 102-114 configured to operate in a flow mode.
• Clause 116 A method which comprises providing additional oxidant to the electrochemical cell of any one of Clauses 102-115.
• Clause 117 The electrochemical cell of Clause 115, further comprising an inflow stream comprising an aqueous electrolyte solution.
• Clause 118 The electrochemical cell of Clause 117, wherein the inflow stream further comprises an oxidant.
• Clause 119 The electrochemical cell of Clause 118, wherein the oxidant is sodium peroxydi sulfate or a solution comprising peroxydi sulfate anion or both.
• Clause 120 The electrochemical cell of any one of Clauses 115-119, wherein an aqueous solution outflows from the cell.
• Clause 121 The electrochemical cell of Clause 120, wherein the aqueous solution outflowing from the cell comprises a metal sulfate.
• Clause 122 The electrochemical cell of Clause 118 or 119, wherein the oxidant is in an aqueous basic solution.
• Clause 123 The electrochemical cell of Clause 122, wherein the base is NaOH.
• Clause 124 The electrochemical cell of Clause 118 or 119 wherein the oxidant is solid Na 2 S 2 0 8 .
• Clause 125 The electrochemical cell of any one of Clauses 115-124, wherein between about 10 Watt-hours/kg of electrolyte and about 100 Watt-hours/kg of electrolyte is produced.
• Clause 126 The electrochemical cell of Clause 125, wherein between about 40 Watt-hours/kg of electrolyte and 80 Watt-hours/kg of electrolyte is produced.
• Clause 127 A method of creating a capacitor comprising the steps of disconnecting the load from one side of the electrochemical cell of any one of Clauses 115-126.
• Clause 128 The method of Clause 127, further comprising the step of reconnecting the load.
• Clause 129 A capacitor, prepared by the process of alternatively disconnecting and reconnecting the load from at least one of the current collector or anode in the cell of any one of Clauses 102-126.
• Clause 130 The electrochemical cell of Clause 125, wherein between about 10 Watt-hours/kg of electrolyte and about 60 Watt-hours/kg of electrolyte is produced.
• An electrochemical cell comprising a single aqueous electrolyte solution in contact with a non-metallic current collector, an oxidant, and a metal solid wherein current travels from the metal solid to the current collector via a load, and wherein the pH is greater or equal to 12.
• Clause 132 The electrochemical cell of Clause 131, wherein the non- metallic current collector is carbon foam, the oxidant is a peroxydi sulfate salt, and the metal solid is aluminum.
• An electrochemical cell comprising a single aqueous electrolyte solution in contact with a non-metallic current collector, an oxidant, and one or more anodes wherein current travels from the one or more anodes to the current collector via a load, and wherein the pH is greater or equal to 10.
• Clause 134 The electrochemical cell of Clause 133, wherein the one or more anodes are a metal.
• Clause 135. The electrochemical cell of Clause 134, wherein the metal is aluminum, gallium, indium, thallium, or an alloy comprising at least one of these.
• Clause 136 The electrochemical cell of any one of Clause 133-135, wherein the anodes are separated by an insulator.
• Clause 137 The electrochemical cell of Clause 135, wherein the anode is aluminum and is in a foil form.
• Clause 138 The electrochemical cell of any one of Clauses 133-137, wherein the pH is 12 or greater.
• first and second electrolyte solutions are in contact with each other and are immiscible, and wherein there is no membrane in between the first and second electrolyte solutions.
• Clause 140 The electrochemical cell of Clause 139, wherein each polar electrolyte solution further comprising a porous stabilizer.
• Clause 141 The electrochemical cell of any one of Clauses 139-140, configured for flow-mode.
• Clause 142 The electrochemical cell of any one of Clauses 139-141, wherein the first polar electrolyte solution is aqueous.
• Clause 143 The electrochemical cell of any one of Clauses 139-142, wherein the oxidant is a Vanadium ion.
• Clause 144 The electrochemical cell of any one of Clauses 139-142, wherein the oxidant is S 2 0 8 2" .
• Clause 145 The electrochemical cell of any one of Clauses 139-142, wherein the oxidant is CIO " .
• Clause 146 The electrochemical cell of any one of Clauses 139-145, wherein the first polar electrolyte solution further comprises a base.
• Clause 147 The electrochemical cell of Clause 146, wherein the base is selected from KOH, NaOH, Ca(OH) 2 , LiOH, RbOH, CsOH, Sr(OH) 2 , and Ba(OH) 2 .
• Clause 148 The electrochemical cell of Clause 147, wherein the base is
• Clause 149 The electrochemical cell of any one of Clauses 146-148, wherein the pH of the first polar electrolyte solution is between about 8 and about 14.
• Clause 150 The electrochemical cell of Clause 149, wherein the pH of the first polar electrolyte solution is between about 11 and about 14.
• Clause 151 The electrochemical cell of any one of Clauses 140-150, wherein the porous stabilizer is borosilicate.
• Clause 152 The electrochemical cell of any one of Clauses 139-151, wherein the separation agent is a salt.
• Clause 153 The electrochemical cell of Clause 152, wherein the salt is calcium chloride.
• Clause 154 The electrochemical cell of Clause 152, wherein the salt is sodium sulfate.
• Clause 155 The electrochemical cell of any one of Clauses 139-154, wherein the cell is configured to operate in a flow mode.
• Clause 156 The electrochemical cell of Clause 155, further comprising an inflow solution comprising an aqueous solution comprising a base, an oxidant, and a separation agent.
• Clause 157 The electrochemical cell of Clause 156, wherein the base is sodium hydroxide, the separate agent is sodium sulfate, and the oxidant 8 2 0 8 2" .
• Clause 158 The electrochemical cell of any one of Clauses 155-157, wherein an aqueous solution comprising base and sodium sulfate outflows from the cell.
• Clause 159 The electrochemical cell of any one of Clauses 155-157, further comprising an outflow solution comprising an aqueous solution of a base.
• Clause 160 The electrochemical cell of Clause 159, wherein the base is sodium hydroxide.
• Clause 161 The electrochemical cell of any one of Clauses 139-160, wherein a current collector is placed within the first electrolyte solution.
• Clause 162 The electrochemical cell of Clause 161, wherein the current collector is a metal.
• Clause 163 The electrochemical cell of Clause 161, wherein the current collector is a non-metal.
• Clause 164 The electrochemical cell of Clause 163, wherein the current collector is carbon foam.
• Clause 165 The electrochemical cell of any one of Clauses 139-164, further comprising glass wool placed in between the first and second polar electrolyte solutions.
• Clause 166 The electrochemical cell of any one of Clauses 139-165, wherein the second polar electrolyte solution comprises an alcohol.
• Clause 167 The electrochemical cell of any one of Clauses 139-166, wherein the suitable metal ion is Zn 2+ .
• Clause 168 The electrochemical cell of any one of Clauses 139-166, wherein the suitable metal ion is Al 3+ .
• Clause 169 The electrochemical cell of any one of Clauses 139-168, wherein the second polar electrolyte solution is an alcoholic solution and further comprises a base.
• Clause 170 The electrochemical cell of Clause 169, wherein the base is KOH.
• Clause 171 The electrochemical cell of Clause 169, wherein the base is NaOH.
• Clause 172 The electrochemical cell of any one of Clauses 169-171, wherein the pH of the second polar electrolyte solution is between about 8 and about 14.
• Clause 173 The electrochemical cell of Clause 172, wherein the pH of the second polar electrolyte solution is between about 11 and about 14.
• Clause 174 The electrochemical cell of any one of Clauses 166-173, wherein the separation agent is a salt and the alcohol is ethanol, methanol, or both.
• Clause 175. The electrochemical cell of Clause 174, wherein the salt is CaCl 2 .
• Clause 176 The electrochemical cell of Clause 174, wherein the salt is sodium sulfate.
• Clause 177 The electrochemical cell of any one of Clauses 166-176, wherein the alcohol is ethanol.
• Clause 178 The electrochemical cell of any one of Clauses 139-177, wherein a current collector is placed within the second electrolyte solution.
• Clause 179 The electrochemical cell of Clause 178, wherein the current collector is a metal.
• Clause 180 The electrochemical cell of Clause 178, wherein the current collector is a non-metal.
• Clause 181 The electrochemical cell of Clause 180, wherein the current collector is carbon foam.
• Clause 182 The electrochemical cell of any one of Clauses 166-181, wherein the cell is configured to operate in a flow mode.
• Clause 183 The electrochemical cell of Clause 182, further comprising an inflow stream comprising a polar solution comprising an alcohol, a base, a separation agent, and a metal capable of dissociating into a suitable metal ion.
• Clause 184 The electrochemical cell of Clause 183, wherein the alcohol is ethanol or methanol or both, the base is sodium hydroxide, and the suitable metal ion is
• Clause 185 The electrochemical cell of any one of Clauses 166-184, further comprising an outflow stream comprising an alcohol, a base, and a separation salt.
• Clause 186 The electrochemical cell of Clause 185, wherein the separation salt is sodium sulfate, and the base is sodium hydroxide.
• Clause 187 The electrochemical cell of Clauses 185 or 186, wherein the alcohol is ethanol.
• Clause 188 The electrochemical cell of any one of Clauses 139-187, wherein hydrogen gas is generated in the second electrolyte solution.
• Clause 189 The electrochemical cell of Clause 188, wherein the hydrogen gas is directed to a hydrogen compressor.
• Clause 190 A battery system comprising one or more electrochemical cells of any one of Clauses 139-189 and a hydrogen compressor.
• Clause 191 The battery system of Clause 190 wherein the hydrogen is used to power a process application.
• Clause 192 The battery system of Clause 191, wherein the process application is a fuel cell.
• first and second electrolyte solutions are in contact with each other and are immiscible, and wherein there is no membrane in between the first and second electrolyte solutions.
• Clause 194 The electrochemical cell of Clause 193, wherein the first polar electrolyte solution and second polar electrolyte solution are of different densities and wherein the first electrolyte solution further comprises a halide salt and the second electrolyte solution further comprises a metal sulfate salt.
• Clause 195 The electrochemical cell of Clause 194, wherein the alcohol is methanol or ethanol, the halide salt is CaCl 2 and the metal sulfate salt is Na 2 S0 4 .
• Clause 196 The electrochemical cell of Clause 195, wherein the pH of the first electrolyte and second electrolyte solutions are adjusted to between about 11 to about 13 each.
• Clause 197 The electrochemical solution of Clause 193, wherein the first and second electrolyte solutions further comprise a base.
• Clause 198 The electrochemical solution of Clause 197, wherein the base is sodium, calcium or potassium hydroxide.
• Clause 199 The electrochemical cell of any one of Clauses 193-198, wherein the cathode is copper, carbon, or both and the anode is aluminum.
• Clause 200 The electrochemical cell of Clause 199, wherein the cathode is a copper brush.
• Clause 201 The electrochemical cell of any one of Clauses 193-200, wherein the borosilicate is Pyrex ® wool.
• Clause 202 The electrochemical cell of any one of Clauses 193-201 wherein the cell is configured to run in a flow mode.
• Clause 203 An electrochemical battery comprising one or more electrochemical cells of any one of Clauses 193-202.
• Clause 204 The electrochemical battery of Clause 203, wherein the number of electrochemical cells is greater than one and the electrochemical cells are arranged in a parallel geometry.
• Clause 205 The electrochemical battery of Clause 204, wherein the cells are arranged in a voltaic pile.
• Clause 206 The electrochemical battery of any one of Clauses 203-205, wherein the battery delivers electricity to a process application.
• Clause 207 The electrochemical battery of Clause 206, wherein the process application is selected from solar farms, wind farms, household appliances, consumer goods, and toys.
• Clause 208 A method of delivering electricity from an electrochemical cell of any one of Clauses 193-202 to a process application.
• Clause 209 The method of Clause 208, wherein the process application is selected from solar farms, wind farms, household appliances, consumer products, and toys.
• Clause 210 The electrochemical cell of Clause 201, wherein the borosilicate has a pore size of about 8 microns.
• An electrochemical cell comprising:
• first and second electrolyte solutions are in contact with each other and are immiscible, and wherein there is no membrane in between the first and second electrolyte solutions.
• Clause 212 The electrochemical cell of Clause 211, wherein the metal solid is dispersed through the solution in powder form and wherein borosilicate is placed within both the first and second electrolyte solutions.
• Clause 213. The electrochemical cell of Clause 212, wherein the metal is zinc.
• Clause 214 The electrochemical cell of Clause 212, wherein the metal is aluminum.
• Clause 21 The electrochemical cell of any one of Clauses 211-214, wherein the non-metallic cathode is carbon foam.
• Clause 216 The electrochemical cell of any one of Clauses 211-215, wherein the non-metallic anode is carbon foam.
• Clause 217 The electrochemical cell of any one of Clauses 212-216 wherein the average particle size of the powder is less than about 5 microns.
• Clause 218 The electrochemical cell of any one of Clauses 212-216, wherein the average particle size of the powder is between about 5 and about 30 microns.
• Clause 219. A method of boosting current in an electrochemical cell comprising the steps of adding oxidant to the second electrolyte solution of any one of Clauses 211-218.
• An electrochemical cell comprising:
• first and second electrolyte solutions are in contact with each other and are immiscible, and wherein there is no membrane in between the first and second solutions.
• Clause 22 The electrochemical cell of Clause 220, wherein the second polar electrolyte solution is an alcoholic solution.
• Clause 222 The electrochemical cell of Clause 221, wherein the alcohol is ethanol or methanol.
• Clause 223 The electrochemical cell of any one of Clauses 220-222, wherein the oxidant is S 2 0 8 2" or sodium peroxydisulfate, or both, the metal is aluminum, the separation agent is sodium sulfate, and the cathode and anode are carbon foam.
• Clause 224 The electrochemical cell of Clause 223, wherein a porous stabilizer is in the first and second electrolyte solutions.
• Clause 225 The electrochemical cell of Clause 224, wherein the porous stabilizer is glass wool, a borosilicate, or both.
• Clause 226 The electrochemical cell of any one of Clauses 220-225, configured to operate in a flow mode.
• Clause 227 A method which comprises providing additional oxidant to the electrochemical cell of any one of Clauses 220-226.
• Clause 228 The electrochemical cell of Clause 226 or 227, further comprising an inflow stream comprising an aqueous electrolyte solution.
• Clause 229. The electrochemical cell of Clause 228, wherein the inflow stream further comprises an oxidant.
• Clause 230 The electrochemical cell of Clause 229, wherein the oxidant is sodium peroxydisulfate or a solution comprising peroxydisulfate anion or both.
• Clause 231. The electrochemical cell of any one of Clauses 226 and 228- 230, wherein an aqueous solution outflows from the cell.
• Clause 232 A method which comprises removing metal sulfate from the electrochemical cell of any one of Clauses 226 and 228-230.
• Clause 233 The electrochemical cell of Clause 229, wherein the oxidant is in an aqueous basic solution.
• Clause 234 The electrochemical cell of Clause 233, wherein the base is NaOH.
• Clause 235 The electrochemical cell of Clause 229 or 230 wherein the oxidant is solid Na 2 S 2 0 8 .
• Clause 236 The electrochemical cell of any one of Clauses 220-235, which produces between about 10 Watt-hours/kg of electrolyte and about 100 Watt- hours/kg of electrolyte.
• Clause 237 The electrochemical cell of Clause 208, wherein between about 40 Watt-hours/kg of electrolyte and about 80 Watt-hours/kg of electrolyte is produced.

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• 2018
  • 2018-03-12 JP JP2019547998A patent/JP7121358B2/ja active Active
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