Patent Application
20150030896
The present disclosure relates in general to batteries. More particularly, the present disclosure provides a sodium-based secondary cell (or rechargeable battery) with a sodium ion conductive electrolyte membrane and a liquid positive electrode solution that comprises a halogen and/or a halide.
Batteries are known devices that are used to store and release electrical energy for a variety of uses. In order to produce electrical energy, batteries typically convert chemical energy directly into electrical energy. Generally, a single battery includes one or more galvanic cells, wherein each of the cells is made of two half-cells that are electrically isolated except through an external circuit. During discharge, electrochemical reduction occurs at the cell's positive electrode, while electrochemical oxidation occurs at the cell's negative electrode. While the positive electrode and the negative electrode in the cell do not physically touch each other, they are generally chemically connected by at least one (or more) ionically conductive and electrically insulative electrolytes, which can either be in a solid state, a liquid state, or in a combination of such states. When an external circuit, or a load, is connected to a terminal that is connected to the negative electrode and to a terminal that is connected to the positive electrode, the battery drives electrons through the external circuit, while ions migrate through the electrolyte.
Batteries can be classified in a variety of manners. For example, batteries that are completely discharged only once are often referred to as primary batteries or primary cells. In contrast, batteries that can be discharged and recharged more than once are often referred to as secondary batteries or secondary cells. The ability of a cell or battery to be charged and discharged multiple times depends on the Faradaic efficiency of each charge and discharge cycle.
While rechargeable batteries based on sodium can comprise a variety of materials and designs, most, if not all, sodium batteries that require a high Faradaic efficiency employ a solid primary electrolyte separator, such as a solid ceramic primary electrolyte membrane. The principal advantage of using a solid ceramic primary electrolyte membrane is that the Faradaic efficiency of the resulting cell approaches 100%. Indeed, in almost all other cell designs, electrode solutions in the cell are able to intermix over time and, thereby, cause a drop in Faradaic efficiency and loss of battery capacity.
The primary electrolyte separators used in sodium batteries that require a high Faradaic efficiency often consist of ionically conductive polymers, porous materials infiltrated with ionically conductive liquids or gels, or dense ceramics. In this regard, many rechargeable sodium batteries that are presently available for commercial applications comprise a molten sodium metal negative electrode, a sodium β″-alumina ceramic electrolyte separator, and a molten positive electrode, which may include a composite of molten sulfur and carbon (called a sodium/sulfur cell). Because these conventional high temperature sodium-based rechargeable batteries have relatively high specific energy densities and only modest power densities, such rechargeable batteries are typically used in certain specialized applications that require high specific energy densities where high power densities are typically not encountered, such as in stationary storage and uninterruptible power supplies.
Despite the beneficial characteristics associated with some conventional sodium-based rechargeable batteries, such batteries may have significant shortcomings. In one example, because the sodium β″-alumina ceramic electrolyte separator is typically more conductive and is better wetted by molten sodium at a temperature in excess of about 270° C. and/or because the molten positive electrode typically requires relatively high temperatures (e.g., temperatures above about 170° or 180° C.) to remain molten, many conventional sodium-based rechargeable batteries operate at temperatures higher than about 270° C. and are subject to significant thermal management problems and thermal sealing issues. For example, some sodium-based rechargeable batteries may have difficulty dissipating heat from the batteries or maintaining the negative electrode and the positive electrode at the relatively high operating temperatures. In another example, the relatively high operating temperatures of some sodium-based batteries can create significant safety issues. In still another example, the relatively high operating temperatures of some sodium-based batteries require their components to be resistant to, and operable at, such high temperatures. Accordingly, such components can be relatively expensive. In yet another example, because it may require a relatively large amount of energy to heat some conventional sodium-based batteries to the relatively high operating temperatures, such batteries can be expensive to operate and energy inefficient.
Thus, while sodium-based rechargeable batteries are available, challenges with such batteries also exist, including those previously mentioned. Accordingly, it would be an improvement in the art to augment or even replace certain conventional sodium-based rechargeable batteries with other sodium-based rechargeable batteries.
The present disclosure provides a sodium-halogen secondary cell. While the described sodium-halogen secondary cell can include any suitable component, in some embodiments, it includes a negative electrode compartment housing a negative, sodium-based electrode. In such embodiments, the cell also includes a positive electrode compartment housing a current collector disposed in a liquid positive electrode solution that includes a halogen and/or a halide. The cell also includes a sodium ion conductive electrolyte membrane that separates the negative electrode from the liquid positive electrode solution.
While the negative electrode can comprise any suitable sodium-based anode, in some embodiments, it comprises a sodium metal that is molten as the cell operates. In other implementations, however, the negative electrode comprises a sodium anode or a sodium intercalating carbon that remains solid as the cell functions. In some such implementations in which the negative electrode remains in a solid state as the cell operates, the cell includes a non-aqueous anolyte solution that is disposed between the negative electrode and the electrolyte membrane.
The sodium ion conductive electrolyte membrane can comprise any membrane (which is used herein to refer to any suitable type of separator) that: selectively transports sodium ions; is stable at the cell's operating temperature; is stable when in contact with the positive electrode solution and the negative electrode (or the non-aqueous anolyte); and otherwise allows the cell to function as intended. Indeed, in some non-limiting implementations, the electrolyte membrane comprises a NaSICON-type membrane (e.g., a NaSELECT® membrane, produced by Ceramatec, in Salt Lake City, Utah) that is substantially impermeable to water. Accordingly, in such implementations, the water impermeable electrolyte membrane can allow the positive electrode solution to comprise an aqueous solution, which would react violently if it were to contact the sodium negative electrode.
The current collector in the positive electrode compartment can comprise any suitable material that allows the cell to function as intended. Indeed, in some non-limiting implementations, the current collector comprises a wire, felt, mesh, plate, foil, tube, foam, or other suitable current collector configuration. Additionally, while the current collector can comprise any suitable material, in some implementations, it includes carbon, platinum, copper, nickel, zinc, a sodium intercalation cathode material (e.g., NaXMnO2), and/or any other suitable current collector material.
The liquid positive electrode solution in the positive electrode compartment can comprise any suitable material that is capable of conducting sodium ions to and from the electrolyte membrane and that otherwise allows the cell to function as intended. Some examples of suitable positive electrode solution materials include, but are not limited to, aqueous (e.g., dimethyl sulfoxide, NMF (N-methylformamide), ethylene glycol, and the like) and non-aqueous (e.g., glycerol, ionic liquid, organic electrolyte, etc.) solvents that readily conduct sodium ions and that are chemically compatible with the electrolyte membrane. Additionally, in some implementations, the positive electrode solution comprises a molten fluorosulfonyl amide (e.g., 1-Ethyl-3-methylimidazolium-(bis(fluorosulfonyl)amide) (“[EMIM][FSA]”.
The positive electrode solution also comprises a halogen and/or halide. Some examples of suitable halogens include bromine, iodine, and chlorine. Similarly, some examples of suitable halides include bromide ions, polybromide ions, iodide ions, polyiodide ions, chloride ions, and polychloride ions. While the halogen/halide can be introduced into the positive electrode solution in any suitable manner, in some embodiments, they are added as NaBr, NaI, or NaCl.
In some implementations, the described cell is modified to limit the amount of free-floating halogen that is present in the positive electrode solution and/or in the positive electrode compartment. While the amount of halogen in the cell can be reduced and/or controlled in any suitable manner, in some implementations, it is done by: including a sufficient amount of a sodium halide (e.g., NaBr, NaI, etc.) and/or an elemental halogen (e.g., bromine, iodine, etc.) to form polyhalides (e.g., Br3−, I3−, etc.) from free halogen molecules in the positive electrode solution; by adding a complexing agent (e.g., tetramethyl ammonium bromide, tetramethyl ammonium iodide, N-methyl-N-methylmorpholinium bromide, N-methyl-N-methylmorpholinium iodide, etc.) that is capable of forming an adduct (or otherwise complexing) with halides, halogens, and/or polyhalides in the positive electrode solution; using a current collector comprising a metal (e.g., copper, nickel, zinc, etc.) that oxidizes to form metal ions that can react with halide ions in the solution to form a metal halide (e.g., CuBr, CuI, NiBr2, NiI2, ZnBr2, ZnI2, etc.) before the halide ions in the solution are oxidized to form the corresponding halogen; and any suitable combination thereof.
In some embodiments where the cell is operated at high temperatures, it may be desirable to have excess sodium halide (e.g., excess I2, Br2) or a complexing agent in order to complex with the formed halogen and keep this component in solution (and not have it convert into a gas). In fact, in some embodiments, up to ⅓ more NaI (sodium halide or complexing agent) may be added to the system. Further, in embodiments that use I2, the casing of the cell may be made of peak stainless steel with Teflon® on the inside, although other less expensive materials, such as other types of stainless steel, may also be used. In yet other embodiments, a cathode chamber may be made of a polyether ether ketone (PEEK) with a Teflon® lining. Teflon® is a registered trademark of the DuPont Company.
In some embodiments, the cell includes a first reservoir that is in fluid communication with the positive electrode compartment. In such embodiments, the reservoir is connected to a pumping mechanism that is configured to force the liquid positive electrode solution to flow from the reservoir and past the current collector in the positive electrode compartment. In some embodiments, the cell also includes a second reservoir that is in fluid communication with the negative electrode compartment. In such embodiments, the reservoir is connected to a pumping mechanism that is configured to force the molten negative electrode (or the non-aqueous anolyte) to flow from the reservoir and through the negative electrode compartment.
The described secondary cell may operate at any suitable operating temperature. Indeed, in some implementations in which the negative electrode is molten as the cell operates, the cell functions (e.g., is discharged or recharged) while the temperature of the negative electrode is between about 100° C. and about 150° C. (e.g., about 120° C.±about 10° C.). Additionally, in some implementations in which the negative electrode remains in a solid state as the cell functions, the temperature of the negative electrode remains below about 60° C. (e.g., about 20° C.±about 10° C.). Further embodiments may be designed in which the cell operates at less than 250° C., or at less than 200° C., or at less than 180° C., or at less than 150° C., etc.
These features and advantages of the present embodiments will become more fully apparent from the following description and appended claims.
Reference throughout this specification to “one embodiment,” “an embodiment,” or similar language means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment,” “in an embodiment,” “in another embodiment,” and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment. Additionally, while the following description refers to several embodiments and examples of the various components and aspects of the described invention, all of the described embodiments and examples are to be considered, in all respects, as illustrative only and not as being limiting in any manner.
Furthermore, the described features, structures, or characteristics of the invention may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided, such as examples of suitable sodium-based negative electrodes, liquid positive electrode solutions, current collectors, sodium ion conductive electrolyte membranes, etc., to provide a thorough understanding of embodiments of the invention. One having ordinary skill in the relevant art will recognize, however, that the invention may be practiced without one or more of the specific details, or with other methods, components, materials, and so forth. In other embodiments, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the invention.
As stated above, secondary cells can be discharged and recharged and this specification describes cell arrangements and methods for both states. Although the term “recharging” in its various forms implies a second charging, one of skill in the art will understand that discussions regarding recharging would be valid for, and applicable to, the first or initial charge, and vice versa. Thus, for the purposes of this specification, the terms “recharge,” “recharged,” and “rechargeable” shall be interchangeable with the terms “charge,” “charged,” and “chargeable,” respectively.
The present embodiments provide a sodium-halogen secondary cell, which includes a negative electrode comprising sodium and a liquid positive electrode solution that comprises at least one of a halogen and a halide. Although the described cell can comprise any suitable component,
Turning now to the manner in which the sodium-halogen secondary cell 10 functions, the cell can function in virtually any suitable manner. In one example,
In a contrasting example,
Referring now to the various components of the cell 10, the cell (as mentioned above) can comprise a negative electrode compartment 15 and a positive electrode compartment 25. In this regard, the two compartments can be any suitable shape or size and have any other suitable characteristic that allows the cell 10 to function as intended. By way of example, the negative electrode compartment and the positive electrode compartments can be tubular, rectangular, or be any other suitable shape. Furthermore, the two compartments can have any suitable spatial relationship with respect to each other. For instance, while
With respect to the negative electrode 20, the cell 10 can comprise any suitable sodium-based negative electrode 20 that allows the cell 10 to function (e.g., be discharged and recharged) as intended. Some examples of suitable sodium-based negative electrode materials include, but are not limited to, a sodium sample that is substantially pure, a sodium alloy comprising any other suitable sodium-containing negative electrode material, and a sodium intercalation material. Indeed, in certain embodiments, the negative electrode comprises or consists of an amount of sodium that is substantially pure. In other embodiments, however, the negative electrode comprises or consists of a sodium intercalation material.
Where the negative electrode 20 comprises a sodium intercalation material, the intercalation material can comprise any suitable material that allows sodium metal in the negative electrode to be oxidized to form sodium ions (Na+) as the cell 10 is discharged, and that also allows sodium ions to be reduced and to intercalate with the intercalation material as the cell is recharged. In some embodiments, the intercalation material also comprises a material that causes little to no increase in the resistance of the electrolyte membrane 40 (discussed below). In other words, in some embodiments, the intercalation material readily transports sodium ions there through and has little to no adverse effect on the rate at which sodium ions pass from the negative electrode compartment 15 to the positive electrode compartment 25 (and vice versa).
In some embodiments, the intercalation material in the negative electrode 20 comprises sodium metal (and/or a sodium metal alloy) intercalated with carbon (e.g., graphite, mesoporous carbon, boron-doped diamond, carbon, and/or graphene). Thus, some embodiments of the negative electrode comprise a sodium intercalating carbon material.
As the cell 10 operates (e.g., discharges and/or charges), the sodium-based negative electrode 20 may be at any suitable temperature that allows the cell to function as intended. Indeed, in some embodiments (e.g., embodiments in which the negative electrode comprises sodium metal), the cell functions at any suitable operating temperature that allows the negative electrode to be molten as the cell functions. Indeed, in some embodiments in which the cell comprises a molten negative electrode, the temperature of the negative electrode as the cell functions (or the operating temperature) is between about 100° C. and about 155° C. In other embodiments, the operating temperature of the cell is between about 110° C. and about 150° C. In still other embodiments, the operating temperature of the cell is between about 115° C. and about 125° C. In yet other embodiments in which the negative electrode is molten as the cell operates, the cell has an operating temperature that falls within any sub-range of the aforementioned operating temperature ranges (e.g., about 120° C.±2° C.). In further embodiments, the cell may operate at higher temperatures, such as less than 250° C., less than 200° C., less than 180° C., etc.
In embodiments in which the negative electrode 20 remains solid as the cell 10 operates (e.g., embodiments in which the negative electrode comprises a sodium intercalating carbon and/or a solid sodium anode), the cell functions at any suitable operating temperature that allows the cell to function as intended. Indeed, in some embodiments in which the negative electrode is solid as the cell functions, the operating temperature of the cell is between about −20° C. and about 98° C. In other such embodiments, the operating temperature of the cell is between about 18° C. and about 65° C. In still other such embodiments, the operating temperature of the cell is between about 20° C. and about 60° C. In still other embodiments, the operating temperature of the cell is between about 30° C. and about 50° C. In yet other embodiments in which the negative electrode remains in a solid state as the cell operates, the cell has an operating temperature that falls within any sub-range of the aforementioned operating temperature ranges (e.g., about 20° C.±10° C.).
Although, in some embodiments (e.g., where the negative electrode 20 is molten as the cell 10 operates), the negative electrode 20 is in direct contact with (and/or wets) the electrolyte membrane 40, in other embodiments (e.g., where the negative electrode remains solid as the cell functions), the negative electrode is optionally not in direct contact with the electrolyte membrane. Indeed,
Where the cell 10 comprises a non-aqueous anolyte solution 65, the anolyte solution can comprise any suitable chemical that is chemically compatible with the negative electrode 20 and the electrolyte membrane 40, and that is sufficiently conductive to allow sodium ions to pass from the negative electrode to the electrolyte membrane and vice versa. In this regard, some examples of suitable non-aqueous anolytes include, but are not limited to, propylene carbonate; ethylene carbonate; one or more organic electrolytes, ionic liquids, polar aprotic organic solvents, polysiloxane compounds, acetonitrile base compounds, etc.; ethylacetate; and/or any other suitable non-aqueous liquid and/or gel. For a more-detailed description of suitable non-aqueous anolyte solutions, see U.S. Patent Application Publication No. 2011/0104526, filed Nov. 5, 2010; the entire disclosure of which is incorporated herein by reference.
With regards now to the sodium ion conductive electrolyte membrane 40, the membrane can comprise any suitable material that selectively transports sodium ions and permits the cell 10 to function with a non-aqueous positive electrode solution 35 or an aqueous positive electrode solution 35. In some embodiments, the electrolyte membrane comprises a NaSICON-type (sodium Super Ion CONductive) material. Where the electrolyte membrane comprises a NaSICON-type material, the NaSICON-type material may comprise any known or novel NaSICON-type material that is suitable for use with the described cell 10. Some suitable examples of NaSICON-type compositions include, but are not limited to, Na3Zr2Si2PO12, Na1+xSixZr2P3−xO12 (where x is between about 1.6 and about 2.4), Y-doped NaSICON (Na1+x+yZr2−yYySixP3−xO12, Na1+xZr2−yYy SixP3−xO12−y (where x=2, y=0.12)), Na1−xZr2SixP3−xO12 (where x is between about 0 and about 3, and in some cases between about 2 and about 2.5), and Fe-doped NaSICON (Na3Zr2/3Fe4/3P3O12). Indeed, in certain embodiments, the NaSICON-type membrane comprises Na3Si2Zr2PO12. In other embodiments, the NaSICON-type membrane comprises one or more NaSELECT® materials, produced by Ceramatec, Inc. in Salt Lake City, Utah. In still other embodiments, the NaSICON-type membrane comprises a known or novel composite, cermet-supported NaSICON membrane. In such embodiments, the composite NaSICON membrane can comprise any suitable component, including, without limitation, a porous NaSICON-cermet layer that comprises NiO/NaSICON or any other suitable cermet layer, and a dense NaSICON layer. In yet other embodiments, the NaSICON membrane comprises a monoclinic ceramic.
In some embodiments (as shown in
While the porous substrate layer 70 can be any suitable thickness, in some embodiments, it is between about 50 μm and about 1250 μm thick. In other embodiments, the porous substrate layer is between about 500 μm and about 1,000 μm thick. In still other embodiments, the porous substrate layer is between about 700 μm and about 980 μm. In still other embodiments, the porous substrate layer has a thickness that falls in any suitable sub-range of the aforementioned ranges (e.g., between about 740 μm and about 960 μm).
The dense layer 75 on the substrate layer 70 can be any suitable thickness that allows the cell 10 to function as intended. Indeed, in some embodiments the dense layer (e.g., a dense layer of a NaSICON-type material) has a thickness between about 20 μm and about 400 μm. In other embodiments, the dense layer has a thickness between about 45 μm and about 260 μm. In still other embodiments, the dense layer has a thickness that falls in any sub-range of the aforementioned thicknesses (e.g., about 50 μm±10 μm).
The electrolyte membrane 40 can have any suitable sodium conductivity that allows the cell 10 to operate as intended. Indeed, in some embodiments (e.g., where the electrolyte membrane comprises NaSELECT® or another suitable NaSICON-type material), the electrolyte membrane has a conductivity of between about 4×10−3 S/cm−1 and about 20×10−3 S cm−1 (or any sub-range thereof).
Where the electrolyte membrane 40 comprises a NaSICON-type material, the NaSICON-type material may provide the cell 10 with several beneficial characteristics. In one example, because NaSICON-type materials, as opposed to a sodium β″-alumina ceramic electrolyte separator, are substantially impermeable to, and stable in the presence of, water, NaSICON-type materials can allow the cell to include a positive electrode solution 35, such as an aqueous positive electrode solution, that would otherwise be incompatible with the sodium negative electrode 20. Thus, the use of a NaSICON-type membrane as the electrolyte membrane can allow the cell to have a wide range of battery chemistries. As another example of a beneficial characteristic that can be associated with NaSICON-type membranes, because such membranes selectively transport sodium ions but do not allow the negative electrode 20 and the positive electrode solutions 35 to mix, such membranes can help the cell to have minimal capacity fade and to have a relatively stable shelf life at ambient temperatures. Indeed, some NaSICON-type materials (e.g., NaSELECT® membranes) eliminate self-discharge, crossover, and/or related system inefficiencies due to the materials' solid-solid perm-selectivity.
With respect to the current collector 30, the cell 10 can comprise any suitable current collector that allows the cell to be charged and discharged as intended. For instance, the current collector can comprise virtually any current collector configuration that has been successfully used in a sodium-based rechargeable battery system. In some embodiments, the current collector comprises one or more wires, felts, foils, plates, parallel plates, tubes, meshes, mesh screens, foams (e.g., metal foams, carbon foams, etc.), and/or other suitable current collector configuration. Indeed, in some embodiments, the current collector comprises a configuration having a relatively large surface area (e.g., one or more mesh screens, metal foams, etc.).
The current collector 30 can comprise any suitable material that allows the cell 10 to function as intended. In this regard, some non-limiting examples of suitable current collector materials include carbon, platinum, copper, nickel, zinc, a sodium intercalation material (e.g., NaXMnO2, etc.), nickel foam, nickel, a sulfur composite, a sulfur halide (e.g., sulfuric chloride), and/or another suitable material. Furthermore, these materials may coexist or exist in combinations. In some embodiments, however, the current collector comprises carbon, platinum, copper, nickel, zinc, and/or a sodium intercalation material (e.g., NaXMnO2).
The current collector 30 can be disposed in any suitable location in the positive electrode compartment 25 that allows the cell 10 to function as intended. In some embodiments, however, the current collector is disposed on (e.g., as shown in
With respect now to the positive electrode solution 35, that solution can comprise any suitable sodium ion conductive material that allows the cell 10 to function as intended. Indeed, in some embodiments, the positive electrode solution comprises an aqueous or a non-aqueous solution. In this regard, some examples of suitable aqueous or water-compatible solutions comprise, but are not limited to, dimethyl sulfoxide (“DMSO”), water, formamide, N-methylformamide (NMF), ethylene glycol, an aqueous sodium hydroxide (NaOH) solution, an ionic aqueous solution, and/or any other aqueous solution that is chemically compatible with sodium ions and the electrolyte membrane 40. Indeed, in some embodiments, positive electrolyte solution comprises NMF, formamide, and/or DMSO.
In some embodiments, the positive electrode solution 35 comprises a non-aqueous solvent. In such embodiments, the positive electrode solution can comprise any suitable non-aqueous solvent that allows the cell 10 to function as intended. Some examples of such non-aqueous solvents include, without limitation, glycerol, ethylene, propylene, and/or any other non-aqueous solution that is chemically compatible with sodium ions and the electrolyte membrane 40.
In some embodiments (e.g., embodiments that comprise a molten sodium negative electrode 20 and a sodium intercalation current collector 30 (e.g., NaxMnO2), as shown in
Where the positive electrode solution 35 comprises Na-FSA, the solution can comprise any suitable fluorosulfonyl amide that is capable of conducting sodium ions to and from the electrolyte membrane and that otherwise allows the cell 10 to function as intended. Some examples of suitable fluorosulfonyl amides include, without limitation, 1-Ethyl-3-methylimidazolium-(bis(fluorosulfonyl)amide (“[EMIM][FSA]”), and other similar chemicals.
In some embodiments, the positive electrode solution 35 also comprises one or more halogens and/or halides. In this regard, the halogens and halides, as well polyhalides and/or metal halides that form therefrom (e.g., where the current collector 30 comprises a metal, such as copper, nickel, zinc, etc. (as discussed below)) can perform any suitable function, including, without limitation, acting as the positive electrode as the cell 10 operates. Some examples of suitable halogens include bromine, iodine, and chlorine. Similarly, some examples of suitable halides include bromide ions, polybromide ions, iodide ions, polyiodide ions, chloride ions, and polychloride ions. While the halogens/halides can be introduced into the positive electrode solution in any suitable manner, in some embodiments, they are added as NaX, wherein X is selected from Br, I, Cl, etc.
In some embodiments in which the positive electrode solution 35 comprises a halogen (“X”) (e.g., bromine or iodine) and/or halide, the cell may have the following reactions as at the negative electrode 20, the positive electrode/current collector 30, and the overall reaction of the cell as it operates:
Negative electrode NaNa++1e−
Positive electrode 2X−X2+2e−
Overall 2Na+X22Na++2X−
Accordingly, where X comprises iodine, the cell 10 may have the following chemical reactions and the following theoretical voltage (V) and theoretical specific energy (Wh/kg):
Na+ + 1e−
I2 + 2e−
2Na+ + 2I−
Additionally, where X comprises bromine, the cell may have the following chemical reactions and the following theoretical voltage and theoretical specific energy:
Na+ + 1e−
Br2 + 2e−
2Na+ + 2Br−
It has been observed that the actual charge transfer reaction at the positive electrode/current collector 30 may occur in at least two steps. These two potential reactions are shown below and designated Battery Chemistry 1 (shown schematically in
3X−
2X3−
2Na+ + 3X−
2Na+ + 2X3−
It will be appreciated that there are at least two potential reactions that occur at the positive electrode/current collector 30, designated by different “Battery Chemistry” numbers
Where X comprises iodine, the cell 10 may have the following chemical reactions and the following theoretical voltage (V vs. SHE (standard hydrogen electrode)) and theoretical specific energy (Wh/kg):
Na+ + 1e−
3I−
2I3−
2Na+ + 3I−
2Na+ + 2I3−
The charging reactions at the positive electrode may occur in two steps: 1) iodide to triiodide and 2) triiodide to iodine. Similarly, discharging reactions at the positive electrode may occur in two steps: 1) iodine to triiodide and 2) triiodide to iodide. Alternatively, the charging and discharging reactions may occur using the combination of reaction chemistries above.
Where X comprises bromine, the cell 10 may have the following chemical reactions and the following theoretical voltage (V vs. SHE) and theoretical specific energy (Wh/kg):
Na+ + 1e−
3Br−
2Br3−
2Na+ + 3I−
2Na+ + 2I3−
The charging reactions at the positive electrode may occur in two steps: 1) bromide to tribromide and 2) tribromide to bromine. Similarly, discharging reactions at the positive electrode may occur in two steps: 1) bromine to tribromide and 2) tribromide to bromide. Alternatively, the charging and discharging reactions may occur using the combination of reaction chemistries above.
The battery chemistry 1, battery chemistry 2, and the combination of battery chemistries 1 and 2 happening at the positive electrode can be chosen or tailored according to several factors, including but not limited to, aqueous and non-aqueous sodium iodide solutions, voltage limits, additives, concentrations of the solution, temperature, the equilibrium between polyiodide and iodine (polybromide and bromine), the presence of free iodine (free brome) at the operating temperature, and the like.
The various ingredients in the positive electrode solution 35 can be present in the cell at any suitable concentrations that allow the cell 10 to function as intended.
In some embodiments, halogens (e.g., bromine, iodine, or chlorine) are formed in the cell 10 as it operates (e.g., charges). In this regard, the halogens can have several effects on the cell as it functions. In one example, halogens produced in the positive electrode solution 35 can have relatively high vapor pressures that, in turn, can expose the cell to undesirable pressures. In another example, halogens in the positive electrode solution can react with other reagents in the solution to form undesirable chemicals (e.g., HOX and/or HX, where the positive electrode solution is aqueous and wherein X is selected from Br, I, etc.). In some implementations, in order to reduce and/or prevent the challenges that can be associated with halogens produced in the positive electrode solution, the cell is modified to reduce the total amount of elemental halogen (e.g., bromine, iodine, etc.) that is present in the positive electrode solution. In such implementations, the cell can be modified in any suitable manner that allows the cell to operate while controlling the amount of halogens that are present in the positive electrode solution.
In some embodiments, to reduce the amount of halogens in the positive electrode solution 35, the solution comprises an excess amount of a sodium halide (e.g., sodium bromide, sodium iodide, sodium chloride, etc.) and/or an excess amount of an elemental halogen (e.g., bromine, iodine, chlorine, etc.). In such embodiments, the positive electrode solution can comprise any suitable amount of the sodium halide and/or the elemental halogen that allows one or more polyhalides (e.g., Br3−, I3−, Cl3−, etc.) to form in the positive electrode solution 35 (as shown in
In some embodiments, to reduce the amount of halogens in the positive electrode solution 35, the positive electrode solution comprises one or more complexing agents that are capable of complexing with or otherwise forming an adduct (e.g., a halide-amine adduct, a halide-ammonium adduct, etc.) with halogens, halides, and/or polyhalides in the positive electrode solution. In this regard, the complexing agent can comprise any chemical that is capable of forming an adduct and/or complex with halogens, halides, and/or polyhalides in the positive electrode solution. Some non-limiting examples of such complexing agents include one or more bromide-amine adducts, iodide-amine adducts, chloride-amine adducts tetramethyl ammonium halides (e.g., tetramethyl ammonium bromide, tetramethyl ammonium iodide, tetramethyl ammonium chloride, etc.), ammonium compounds, N-methyl-N-methylmorpholinium halide, etc. Indeed, in some embodiments in which the positive electrode solution comprises NaBr/Br2, the complexing agent comprises tetramethyl ammonium bromide, which reacts with bromine to form tetramethyl ammonium tri-bromide. In some other embodiments (e.g., embodiments in which the negative electrode compartment 15 comprises a non-aqueous anolyte 65, the positive electrode solution 35 comprise NaBr/Br2, and the current collector 30 comprises carbon, as shown in
In still other embodiments, in order to reduce the amount of halogen produced in the positive electrode solution 35, the cell 10 circumvents the generation of halogens (e.g., bromine, iodine, chlorine, etc.) by utilizing a metal current collector 30 that forms a metal halide that corresponds to the metal used in the current collector and the halide ions in the solution. While such a process can be performed in any suitable manner, in some embodiments, it relies on the metal in the current collector being oxidized before the halide ions in the positive electrode solution are oxidized to form a corresponding halogen. Thus, the result is the formation of a non-volatile metal halide (e.g., CuBr, NiBr2, ZnBr2, CuI, NiI2, ZnI2, etc.). In this regard, the current collector can comprise any suitable metal that is capable of circumventing the generation of a halogen by forming a metal halide as the cell operates. Some non-limiting examples of such metals include copper, nickel, zinc, combinations thereof, and alloys thereof. In this regard, some examples of corresponding half-cell reactions for cells comprising such metal current collectors include the following:
Cu+X−CuX+1e−
Ni+2X−NiX2+2e−
Zn+2X−ZnX2+2e−
Additionally, one example of a full-cell reaction for a NaBr/Br2 cell 10 comprising a nickel current collector 30 is as follows:
2Na+NiBr22NaBr+Ni
While cells comprising metal current collectors 30 can generate a wide variety of voltage ranges, in some cases in which the cell 10 comprises NaBr/Br2 in the positive electrode solution 35 and the current collector comprises copper, nickel, or zinc, the voltage produced by such a cell is about 2.57V, about 2.61V, and about 2V, respectively.
In still some other embodiments, to reduce the total amount of halogen (e.g., bromine, iodine, etc.) in the positive electrode compartment 25, the cell 10 is modified to include any suitable combination of the aforementioned techniques. By way of non-limiting example, some embodiments of the cell include a current collector 30 comprising copper, nickel, zinc, or another suitable metal, and the positive electrode solution 35 comprises a complexing agent, an excess amount of a sodium halide, and/or an excess amount of an elemental halogen.
With reference now to the terminals 45 and 50, the cell 10 can comprise any suitable terminals that are capable of electrically connecting the cell with an external circuit (not shown), including without limitation, to one or more cells. In this regard, the terminals can comprise any suitable material, be of any suitable shape, and be of any suitable size.
Referring now to
Now, referring to the pumping mechanism 60, the cell 10 can comprise any suitable pumping mechanism that is capable of forcing fluids to flow from a reservoir 55 and into the cell. Indeed,
Where the cell 10 is connected to one or more pumping mechanisms (e.g., 60 and 62) and/or reservoirs (e.g., 55 and 56), the pumping mechanisms can be configured to force fluids through the cell (e.g., the positive electrode compartment 25 and/or the negative electrode compartment 15) at any suitable rate that allows the cell to function as intended. In this regard, the specific flow rates of the various embodiments of the cell will depend on the solubility of the various species in the positive electrode solution 35, the components of the negative electrode compartment 15, and/or upon the cells' intended charge and/or discharge rates.
It should be noted that the pumping mechanisms (e.g., 60 and 62) and/or reservoirs (e.g., 55 and 56) may be added to other embodiments, in addition to that which is shown in
In another example, while the negative electrode compartment 15 and the positive electrode compartment 25 can be any suitable size,
In addition to the aforementioned components, the cell 10 can optionally comprise any other suitable component and characteristic. By way of non-limiting illustration
As still another example of another suitable component that can be used with the cell 10, some embodiments of the cell comprise one or more collectors (not shown) between the reservoir 55 and the positive electrolyte compartment 25. While such collectors can perform any suitable function, in some embodiments, the collectors are used to collect halogens (e.g., bromine, iodine, etc.) from the liquid positive electrode solution 35 as the solution flows through the collectors.
In still another example, the cell 10 can be modified in any suitable manner that allows it to accommodate the transfer of sodium from the negative electrode compartment 15 to the positive electrode compartment 25 during discharge. In this regard, some embodiments of the described cell 10 comprise a volume compensating cell casing (not shown).
In another example, the positive electrode solution 35 can comprise any other suitable ingredient that allows the cell 10 to function as described herein. Indeed, in some embodiments, the positive electrode solution comprises carbon (e.g., ground carbon, a carbon containing material, etc.), and/or any other material that allows the solution to be sodium conductive and to be chemically compatible with the electrolyte membrane 40 and the current collector 30.
In yet another example, the cell 10 can be modified in any suitable manner that allows the safety of the cell to be improved while still allowing the cell to function as intended. Indeed, in some embodiments, the cell comprises one or more pressure relief values (not shown). In other embodiments, the cell comprises one or more protective outer covers. In still other embodiments, the cell is divided into 2 or more smaller cells to reduce any dangers that can be associated with a cell that is damaged or malfunctioning. In yet other embodiments, in addition to the electrolyte membrane 40, the cell comprises one or more additional separators between the negative electrode 20 and the positive electrode solution 35 to minimize the possible exposure that can occur between the negative electrode and the positive electrode solution if the electrolyte membrane becomes damaged.
In still another example of how the cell 10 can be modified, some embodiments of the cell include a pressure management system that is configured to control pressure in a portion of the cell, including without limitation, the positive electrode compartment 25 and/or the negative electrode compartment 15. While this pressure management system can perform any suitable function, in some embodiments, it helps maintain a sufficiently high pressure in the positive electrode compartment to retain halogens in solution such that the halogens can chemically react with other chemical species (e.g., excess sodium halides, excess elemental halogen, one or more complexing agents, metal ions from the current collector 30, etc.) in the positive electrode solution 35.
In addition to the aforementioned benefits of the cell 10, the described cell may have several other beneficial characteristics. By way of example, by being able to operate in a temperature range below about 150° C., the cell 10 may operate at significantly lower operating temperatures than some conventional molten sodium rechargeable batteries. Accordingly, the described cell may require less energy to heat and/or dissipate heat from the cell as the cell functions, may be less dangerous use or handle, and may be more environmentally friendly. Additionally, while some conventional sodium rechargeable batteries that operate at relatively high temperatures require relatively expensive construction materials (e.g., metal or ceramic components, glass seals, and/or thermal expansion-matched components), some embodiments of the described cell can be created using less-expensive materials (e.g., polymeric materials, epoxies, epoxies and/or plastic mechanical sealing components, such as the O-rings 85, caps 90, tube flanges 92, etc. shown in
In another example, some embodiments of the described cell 10 are capable of maintaining themselves at a suitable operating temperature through Joule heating. As a result, such cells may allow for relatively high efficiencies, as additional energy may not be required to maintain such cells at high operating temperatures.
In another example, some embodiments of the described cell 10 have a relatively high theoretical cell voltage (e.g., between about 3.23V and about 3.79V), when compared to some competing conventional batteries (e.g., to some Na/S batteries that have a theoretical voltage of about 2.07V and some Zn/Br2 batteries that have a theoretical voltage of about 1.85V). Additionally, some embodiments of the described cell have a relatively high theoretical specific energy (e.g., about 987 Wh/kg for a NaBr/Br2 cell and about 581 Wh/kg for a NaI/I2 cell) when compared with some competing cells (e.g., some Na/S rechargeable batteries that have a theoretical specific energy of about 755 Wh/kg or some conventional Zn/Br2 rechargeable batteries that have a theoretical specific energy of about 429 Wh/kg). Similarly, some embodiments of the described cell have relatively high practical specific energies (e.g., between about 330 and about 440 for some NaBr/Br2 embodiments the cell) when compared to some competing conventional batteries (e.g., some Na/S batteries having a practical specific energy between about 150 and about 240 Wh/kg and some Zn/Br2 batteries that have a practical specific energy of about 65 Wh/kg).
As a result of the relatively high voltage and specific energies associated with some embodiments of the described cell 10, fewer of such embodiments may be needed to achieve the same voltages and specific energies that are obtained by competing conventional batteries. In this regard, using fewer cells can reduce the amount of cell interconnect hardware and charge-control circuitry that is required to obtain a desired voltage and target specific energy. Thus, some embodiments of the described cells can reduce overall battery complexity and total cost through the elimination of cells, interconnect hardware, and charge control circuitry. Additionally, as a result of the cells' relatively high capacities and voltages, such cells may be useful for a wide variety of applications, including, without limitation, in grid-scale electrical energy storage systems and in electrical vehicles.
In still another example of a beneficial characteristic, some embodiments of the described cell 10 may have relative long cycle lives when compared to some competing batteries (e.g., about 5,000 deep cycles for some NaBr/Br2 embodiments of the cell, as opposed to about 4,000 cycles for some Na/S batteries and about 2,000 for some Zn/Br2 batteries). Additionally, as some embodiments of the described cell are capable of the extensive utilization of sodium and a halogen during cycling, the discharge/charge cycles of such embodiments can be relatively deep (e.g., having a high SOC (state of charge) and DOD (depth of discharge) of between about 70% and about 80%) compared to some conventional batteries.
In still another example, some embodiments of the described cell 10 produce relatively high currents (and hence power) because of the high mobility of sodium ions through the electrolyte membrane 40 (e.g., a fully dense NaSICON-type material on a porous support) and the relatively fast kinetics of the redox reactions—especially at the low and intermediate temperatures described herein (e.g., ambient temperature to about 150° C.).
Referring now to
The positive electrode compartment 25 includes a current collector 30, which in this case may be a carbon current collector, although other types of materials (such as metals) may be used. A liquid positive electrode solution 35 is also housed in the positive electrode compartment 25. In the embodiment of
The embodiment of
With respect to
Br2+tetramethyl ammonium bromide⇄tetramethyl ammonium tribromide
In one embodiment, the membrane is a NaSICON tubes that allows the battery system to be pressurized. Pressure could be used to keep the bromine in solution form.
Referring now to
Cu+Br−⇄CuBr+e−
Ni+2Br−⇄NiBr2+2e−
Zn+2Br−⇄ZnBr2+2e−
An example of a full cell reaction is:
2Na+NiBr2⇄2NaBr+Ni
This cell 10 relies on oxidation of the current collector 30 metal before the oxidation of bromide ion to bromine so the result is the formation of non-volatile metal bromide. The voltages for these batteries may be 2.57, 2.61 and 2 volts respectively for Cu, Ni and Zn. The battery may include a bromide or bromine electrode, a complexing agent, and an aqueous or non-aqueous solvent at 120° C. The battery may have a NaSICON membrane that is stable in these conditions.
Referring now to
The cell 10 of
One particular embodiment of the cell 10 shown in
Referring now to
In this cell 10, the Zn anode 20b will be placed in an aqueous solution containing sodium bromide (or another solution of alkali metal ions and halide ions). The anode shown in this Figure is Zn, but other metals may also be used. The liquid positive electrode solution 35 (catholyte) will be a bromine/sodium bromide solution with a graphite current collector. During discharge, Zn will oxidize to form Zinc bromide and the sodium ions will be transported to the cathode current collector where they react with bromine to form sodium bromide. During charge, Zn will redeposit and bromine is regenerated. The advantages of this cell 10 compared to a microporous type battery are:
(1) The composition of the anolyte can be adjusted to allow reversible deposition of Zn. In fact, the anolyte can be a mixture of NaBr and NaOH so that no zinc dendrites can be formed resulting in loss of capacity;
(2) No self-discharge because the bromine from catholyte will never come into contact with the zinc metal;
(3) Unique electrolyte chemistries may be employed to circumvent the need for flow of the anolyte and catholyte;
(4) Other lower reduction potential elements such as Mg can be used if a nonaqueous solvent are used resulting in a higher voltage battery.
The cell 10 of this embodiment will have a Zn anode in sodium bromide and/or sodium hydroxide solution in a NaSICON based cell and will be capable of reversible deposition. The NaSICON membrane in this battery will be stable in the presence of bromide/bromine/complexing agent/aqueous or non-aqueous solvent at ambient temperature.
The cell 10 may be configured to have reversible NaBr/Br2 cathode operation at ambient temperature. This cell 10 may have at least twenty five reversible cycles at practical C-rates (C/5) and practical Depth of Discharge (DOD>50%) in a stagnant battery with Zn anode and NaBr/Br2 cathode.
The following examples are given to illustrate various embodiments within, and aspects of, the scope of the present invention. The examples are given by way of example only, and it is understood that the following examples are not comprehensive or exhaustive of the many types of embodiments that can be prepared.
In one example, a cell 10 was set up to include a molten sodium negative electrode 20, a platinum mesh current collector 30, a positive electrode solution comprising 20 wt % NaI in formamide with a 1:3 molar ratio of I2 to NaI+5 wt % carbon from the formamide as the positive electrode. In this example, after operating at a temperature up to about 120° C. for over 2,000 minutes, the cell had the performance characteristics shown in
In a second example, a cell 10 was set up to include a molten sodium negative electrode 20, a platinum mesh current collector 30, a positive electrode solution comprising up to about 25 wt % NaI and more than about 75% DMSO, with a NaSICON-type membrane having a current density of between 5 mA/cm2 and 10 mA/cm2. In this example, after operating at a temperature up to about 120° C. for over 150 hours, the cell had the performance characteristics shown in
In a third example, a first large cell was set up to include an electrolyte membrane 40 having a current density of about 3.65 mA/cm2 and having approximately 4 times the surface area of the membranes used in the first two examples, a molten sodium negative electrode 20, a platinum mesh current collector 30, and a positive electrode solution 35 comprising up to about 25 wt % NaI and more than about 75 wt % formamide with 0.5 moles of I2 per mole of NaI. Additionally, a second large cell was set up to include an electrolyte membrane 40 having a current density of about 3.65 mA/cm2 and with approximately 4 times the surface area of the membranes used in the first two examples, a molten sodium negative electrode 20, a platinum mesh current collector 30, a positive electrode solution 35 comprising up to about 25 wt % NaI and more than about 75 wt % DMSO with 0.5 moles of I2 per mole of NaI. These two cells were operated at a temperature of up to about 120° C. for more than 120 hours with a depth of discharge of about 20% of the cells' available capacity. The performance characteristics of the cell using DMSO solvent are displayed in
In one example, a cell 10 was set up to include a molten sodium negative electrode 20, an electrolyte membrane 40 comprising a NaSICON-type membrane having a current density of approximately 10 mA/cm2, and a positive electrode solution 35 comprising NaI/I2 dissolved in formamide solvent with added carbon. The cell was then operated at about 110° C. for over 30 hours. Some performance characteristics of a test run of this experimental cell are shown in
In one example showing the battery chemistry 1 and battery chemistry 2, where the halogen is iodine, a standard electrochemical cyclic voltammetry (CV) method was used to study oxidation of near neutral pH sodium iodide solution. The test setup includes three platinum electrodes (one reference, one counter and one working) immersed in an aqueous solution of 0.2M NaI/0.1M I2. The test was conducted at ambient temperature. During the test, the cell voltage is gradually increased and decreased versus the cell open circuit voltage and the working electrode potential was measured using the reference electrode. Also measured was the cell current generated by the reactions at the working and counter electrodes.
3NaI→NaI3+2Na++2e−
Next oxidation peak at 0.8V occurs due to oxidation of triiodide to molecular iodine according to the reaction of battery chemistry 2, described above:
NaI3→3/2I2+Na++e−
This data shows that it is easier to oxidize sodium iodide to triiodide, which when coupled with molten Na will result in lower voltage battery chemistry 1 (open circuit voltage of 2.8V) compared to the oxidation of triioidide to iodine, which results in higher voltage battery chemistry 2 (open circuit voltage of 3.15V).
In one example of battery chemistry, a 263 mAh cell was set up to include a molten sodium negative electrode, an electrolyte membrane comprising a NaSICON-type membrane having a current density of approximately 8.8 mA/cm2, and a positive electrode solution comprising 35 wt. % NaI dissolved in NMF solvent (no I2). The cell was then operated at about 110° C. for over 24 hours. Some performance characteristics of a test run of this experimental cell are shown in
In one example, a 263 mAh cell was set up to include a molten sodium negative electrode, an electrolyte membrane comprising a NaSICON-type membrane having a current density of approximately 7.5 mA/cm2, and a positive electrode solution comprising 35 wt. % NaI dissolved in NMF solvent (no I2). The cell was then operated at about 110° C. for about 200 hours. Some performance characteristics of a test run of this experimental cell are shown in
In one example, a 263 mAh cell was set up to include a molten sodium negative electrode, an electrolyte membrane comprising a NaSICON-type membrane having a current density of approximately 3.8 mA/cm2, and a positive electrode solution comprising 35 wt. % NaI dissolved in NMF solvent (no I2). The cell was then operated at about 110° C. over three charge/discharge cycles. Some performance characteristics of a test run of this experimental cell are shown in
In one example, two cells were set up to include a molten sodium negative electrode, an electrolyte membrane comprising a NaSICON-type membrane having a current density of approximately 8.3 mA/cm2, and a positive electrode solution comprising 7M I2 (precharged with excess iodine) and 3M NaI dissolved in NMF solvent or DMSO solvent. The cells were then discharged at about 120° C. The discharge characteristics of a test run of these experimental cells are shown in
Thus, the above-recited examples show that a Na-Iodine battery may be implemented that uses DMSO or NMF as the solvent to dissolve the sodium iodide and (at least partially) dissolve the iodine. This system may be capable of deep discharge of about 50% of available capacity of NaI/Iodine cathode and possibly up to about 70% of available capacity of NaI/iodine cathode making it a practical battery system. In some embodiments, a Pt cathode may be replaced with a lower-cost cathode such as graphite, hard carbon or metals such as manganese, molybdenum, tungsten, titanium, tantalum and other valve metals. The membrane used in the cells may be a NaSICON membrane and may have a current density that is greater than or equal to 10 mA/cm2.
The batteries (cells) that are described herein may have significant advantages over other types of batteries. For example, as noted above, many types of known sodium rechargeable batteries must be operated at high temperatures, such as, for example, above 250° C. or even above 270° C. However, as noted herein, the present embodiments may be operated at temperatures below 250° C. In fact, some embodiments may be operated at ambient temperatures, at temperatures less than about 60° C., at temperatures less than about 150° C., less than 200° C., less than 180° C., etc. These temperature ranges for batteries can provide significant benefits as resources do not have to be allocated to heat the batteries to extreme high temperatures (such as 270° C.).
Further, some of the present embodiments may use NaSICON in lieu of sodium β″-alumina ceramic materials as the separator. NaSICON has specific advantages over sodium β″-alumina ceramics as the NaSICON is compatible with water and other solvents. Further, NaSICON can separate the two sides of the cell such that each side may be optimized without worrying that the reactants on one side of the membrane will foul/interfere with the reactants on the other side of the membrane.
All the patent applications and patents listed herein are expressly incorporated herein by reference.
Embodiments of the present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments and examples are to be considered in all respects only as illustrative and not as restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/888,933 entitled “NASICON MEMBRANE BASED Na—I2 BATTERY,” filed Oct. 9, 2013. This application is a continuation-in-part of U.S. patent application Ser. No. 14/019,651, entitled “SODIUM-HALOGEN BATTERY,” filed Sep. 6, 2013, which claims the benefit of U.S. Provisional Patent Application Ser. No. 61/697,608 entitled “SODIUM-HALOGEN BATTERY,” filed Sep. 6, 2012, and which also claims the benefit of U.S. Provisional Patent Application Ser. No. 61/777,967 entitled “SODIUM-HALOGEN SECONDARY CELL,” filed Mar. 12, 2013, and which also claims the benefit of U.S. Provisional Patent Application Ser. No. 61/781,530 entitled “SODIUM-HALOGEN SECONDARY FLOW CELL,” filed Mar. 14, 2013, and which also claims the benefit of U.S. Provisional Patent Application Ser. No. 61/736,444 entitled “BATTERY WITH BROMINE OR BROMIDE ELECTRODE AND SODIUM SELECTIVE MEMBRANE,” filed Dec. 12, 2012. All of these prior patent applications are expressly incorporated herein by reference.
This invention was made with government support under Contract No. 1189875 awarded by the Sandia National Lab. The government has certain rights in the invention.
| Number | Date | Country | |
|---|---|---|---|
| 61888933 | Oct 2013 | US | |
| 61697608 | Sep 2012 | US | |
| 61777967 | Mar 2013 | US | |
| 61781530 | Mar 2013 | US | |
| 61736444 | Dec 2012 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 14019651 | Sep 2013 | US |
| Child | 14511031 | US |
