Rechargeable hybrid sodium metal-sulfur battery

Abstract

The present technology provides rechargeable alkali metal-sulfur galvanic cells, batteries incorporating such cells, and methods of using such cells and batteries. The galvanic cells provide high specific energy and high power output at lower cost than conventional alkali metal-sulfur cells.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Application No. 62 / 985,250, filed on 4 March 2020, which is incorporated herein by reference in its entirety. [Background technology]

[0002] background Sodium-sulfur (Na-S) batteries offer high energy density with acceptable safety, power density, and cost. The theoretical specific energy of a sodium-sulfur battery is given by the following overall reaction: Based on TIFF0007926915000001.tif4128, the value is 1273 Wh / kg. This is one of the highest known gravimetric energy densities for rechargeable batteries. The electrode materials (sodium and sulfur) required to manufacture these batteries are lightweight, energetic, inexpensive, and readily available. In contrast to other types of positive electrode materials, sulfur is relatively non-toxic, thereby making these batteries relatively safe for human contact. When sulfur is used as the positive electrode and sodium as the negative electrode, the battery can produce an output of approximately 2.3V, representing the open-circuit voltage in the charged state. Similarly, when Na2S is used as the positive electrode active material and sodium as the negative electrode, the battery can produce an output of approximately 2V, representing the open-circuit voltage in the discharged state.

[0003] Commercially available sodium-sulfur batteries operate at high temperatures exceeding 300°C. Such temperatures are required to provide practical ionic conductivity with the sodium β''-alumina ceramic membranes typically used in sodium-sulfur batteries. At such temperatures, both the sodium negative electrode and the sulfur / polysulfide positive electrode are in a molten state, and no solvent is required to dissolve the positive electrode active material. Nevertheless, the high operating temperature causes safety issues, requires higher-cost materials for cell housings and complex thermal management systems, and limits the use of this technology to large-scale stationary installations.

[0004] Lower-temperature Na-S battery technology has been explored for some time, but such technologies have also presented new challenges. Ambient temperature Na-S batteries often suffer from low reversible capacity, self-discharge, and severe cycling problems. At intermediate temperatures (e.g., 100 to 200°C), Na-S batteries can suffer from low ionic conductivity of ceramic membranes and low power density. In addition, reliance on polar aprotic electrolytes is necessary due to the increased insolubility of higher-order polysulfides (e.g., Na2S4 and Na2S5) in the intermediate temperature range. At the same time, the irreversible formation of lower-order polysulfides (e.g., Na2S2 and Na2S3) and sulfur causes capacity fade and cell failure, leading to insufficient utilization of sulfur positive electrode active material during cell operation. Summary of the Invention

[0005] Summary The present technology provides rechargeable sodium-sulfur galvanic cells, batteries incorporating such cells, and methods of using such cells and batteries. The galvanic cells provide higher specific energy and higher power output at lower cost than conventional sodium metal-sulfur cells.

[0006] In one embodiment, the technology provides a rechargeable galvanicell comprising a negative electrode chamber containing a negative electrode active material. The negative electrode active material comprises a liquid alkali metal, the alkali metal being selected from the group consisting of sodium and sodium alloys. The negative electrode chamber is in fluid communication with a first reservoir so that the liquid alkali metal can flow passively between the negative electrode chamber and the first reservoir when the galvanicell is charged or discharged. The cell comprises a positive electrode chamber containing a mixture of a positive electrode active material and a positive electrolyte. Depending on the charge state of the galvanicell, the positive electrode active material comprises elemental sulfur and / or polysulfide (Na2S x The formula includes ), where x has a value of 1 to 32. The positive electrolytes are sulfur and Na2S. x The solution contains a polar organic solvent, optionally containing a polar protic organic solvent, which partially or completely dissolves the material. The positive electrode chamber is in fluid communication with the pump and the second reservoir so that during charging or discharging of the galvanic cell, the pump can circulate the positive electrode active material and positive electrolyte between the second reservoir and the positive electrode chamber. The cell further includes a sodium ion conductive ceramic film separating the negative electrode chamber from the positive electrode chamber.

[0007] In another embodiment, the technology provides a battery comprising one or more rechargeable galvanic cells described herein.

[0008] In yet another embodiment, the Art provides a method for operating a rechargeable galvanicell as described herein. The method includes charging or discharging the galvanicell while circulating a mixture of a positive electrolyte and a positive electrode active material from a second reservoir through a positive electrode chamber back to the second reservoir. If the negative electrode active material is sodium or a sodium alloy, the method may further include heating the mixture to a temperature of about 100°C to about 200°C before the mixture enters the positive electrode chamber. The method may further include cooling the mixture to a temperature of less than 100°C after the mixture has left the positive electrode chamber. [Invention 1001] It is a rechargeable galvanic cell, and the following: A negative electrode chamber containing the negative electrode active material, The negative electrode active material contains a liquid alkali metal, and the alkali metal is selected from the group consisting of sodium and sodium alloys, The negative electrode chamber is in fluid communication with the first reservoir so that the liquid alkali metal can passively flow between the negative electrode chamber and the first reservoir when the galvanicellum is being charged or discharged. Negative electrode chamber; A positive electrode chamber containing a mixture of positive electrode active material and positive electrolyte, The positive electrode active material contains elemental sulfur and / or Na, depending on the charge state of the galvanicellum. 2 S x The formula includes, where x has values ​​from 1 to 32. The positive electrolyte is the Na 2 S x A polar organic solvent, which optionally contains a polar protic organic solvent, partially or completely dissolves the substance, and During charging or discharging of the galvanicellum, the positive electrode chamber is in fluid communication with the pump and the second reservoir so that the pump can circulate the positive electrode active material and positive electrolyte between the second reservoir and the positive electrode chamber. Positive electrode chamber; and A sodium ion conductive ceramic film separates the negative electrode chamber from the positive electrode chamber. Includes a rechargeable galvanic cell. [Invention 1002] The rechargeable galvanic cell according to the present invention 1001, wherein the negative electrode active material is sodium. [Invention 1003] A rechargeable galvanic cell according to the present invention 1001 or 1002, further comprising a heat source for maintaining the temperature of the ceramic film, the negative electrode active material, and / or the positive electrode active material and positive electrolyte at a temperature of about 100°C to about 200°C. [Invention 1004] The aforementioned heat source, A heat exchanger that is in fluid communication with the positive electrode chamber and heats the positive electrolyte to a temperature of approximately 100°C to approximately 200°C before the positive electrolyte enters the positive electrode chamber. The rechargeable galvanic cell of the present invention 1003. [Invention 1005] A rechargeable galvanicell of any of the present inventions 1001 to 1003, wherein the sodium ion conductive ceramic film comprises, essentially consists of, or comprises at least one of NaSICON, sodium ion conductive garnet-like ceramic, sodium β''-alumina, and sodium conductive glass ceramic. [Invention 1006] A rechargeable galvanic cell according to any of the present invention 1001 to 1005, wherein the positive electrolyte has a conductivity of at least 30 mS / cm at a temperature of about 100°C to about 200°C. [Invention 1007] A rechargeable galvanic cell according to any of the present invention 1001 to 1006, wherein the polar organic solvent comprises one or more polar protic solvents. [Invention 1008] The rechargeable galvanicell of the present invention 1007, wherein the polar protic solvent is selected from the group consisting of alcohols, thiols, primary amides, and secondary amides, and any two or more mixtures thereof. [Invention 1009] A rechargeable galvanicellent according to any of invention 1001 to 1008, wherein the polar organic solvent comprises one or more of 3-propanediol, 2,3-butanediol, 1,4-butanediol, dihydroxybenzyl alcohol, cyclopentane-1,2-diol, cyclopentane-1,3-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, diethylene glycol, triethylene glycol, and tetraethylene glycol. [Invention 1010] A rechargeable galvanic cell according to any of the present invention 1001 to 1009, wherein the polar organic solvent contains ethylene glycol. [Invention 1011] The aforementioned polar organic solvent Alcohol and, A solvent selected from the group consisting of water, acetic acid, acetamide, ammonium hydroxide, tetramethylammonium hydroxide, and 1,3-propanedithiol. A rechargeable galvanic cell according to any of the present invention 1007 to 1010, including the present invention. [Invention 1012] A rechargeable galvanic cell according to any of the invention 1001 to 1011, wherein the positive electrolyte comprises a larger amount of alcohol, or an alcohol and another polar protic solvent, and a smaller amount of polar aprotic solvent. [Invention 1013] The rechargeable galvanicell of the present invention 1012, wherein the polar aprotic solvent comprises, essentially consists of, or comprises at least one of dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl carbonate, diethyl carbonate, tetraglyceride, and diglyme. [Invention 1014] A rechargeable galvanic cell according to any of the invention 1001 to 1011, wherein the positive electrolyte comprises 40-96% ethylene glycol, 0-20% by weight of water, and 1-40% by weight of NMP. [Invention 1015] A positive electrode current collector is disposed within the positive electrode chamber and electrically connected to the positive electrode active material. A rechargeable galvanic cell according to any of the present invention 1001 to 1014, further comprising the above. [Invention 1016] The rechargeable galvanic cell of the present invention 1015, wherein the positive electrode current collector includes, is essentially made of, or consists of nickel foam, nickel mesh, carbon foam, or carbon felt. [Invention 1017] A rechargeable galvanicell of any of invention 1001 to 1016, wherein the positive electrolyte further comprises a conductivity enhancer selected from the group consisting of sodium halide, sodium carboxylate, sodium sulfur oxygenate, NaOH, NaOCN, sodium carbonate, and any two or more combinations thereof. [Invention 1018] The aforementioned conductivity improving agent is NaI, NaCl, NaBr, NaOH, HCOONa, CH 3 COONa, Na 2 CO 3 NaOCN, Na 2 SO 4 kaNa 2 SO 3 kaNa 2 S 2 O 3 A rechargeable galvanic cell of the present invention 1017, selected from the group consisting of, and any two or more combinations thereof. [Invention 1019] A rechargeable galvanic cell according to any of the present invention 1001 to 1018, wherein the first reservoir and the second reservoir are sized to hold the respective electrode active material sufficient for about 1 to about 50 hours of discharge operation of the cell. [Invention 1020] A rechargeable battery comprising, essentially consisting of, or comprising one or more rechargeable galvanic cells according to any of the invention 1001 to 1019. [Invention 1021] A method for operating a rechargeable galvanic cell according to any of the present invention 1001 to 1020, The galvanicell is charged or discharged while circulating the mixture of the positive electrolyte and the positive electrode active material back from the second reservoir through the positive electrode chamber to the second reservoir, If the negative electrode active material is sodium or a sodium alloy, the mixture is heated to a first temperature of about 100°C to about 200°C before or when it enters the positive electrode chamber. After the mixture has left the positive electrode chamber, the mixture is cooled to a second temperature lower than the first temperature. A method that includes, essentially consists of, or comprises. [Invention 1022] The method of the present invention 1021, comprising heating the mixture to a temperature of about 125°C to about 175°C. [Invention 1023] A method according to the present invention 1021 or 1022, comprising heating the mixture to a temperature of about 125°C to about 150°C. [Invention 1024] Any method of the present invention 1021 to 1023, comprising cooling the mixture from about 80°C to a temperature below 100°C or below 115°C after the mixture has exited the positive electrode chamber. [Brief explanation of the drawing]

[0009] [Figure 1A]This is a schematic diagram of a galvanicellum that exemplifies this technology. [Figure 1B] This is a schematic diagram of a system incorporating the galvanic cell of this technology. [Figure 2] The graphs show the conductivity of various Na2Sx compounds in ethylene glycol, an exemplary polar protic solvent of this technology. [Figure 3] The charge-discharge curve for the first cycle of a molten Na-NaSICON-Na2S hybrid flow cell, which is an exemplary embodiment of this technology, is shown. [Figure 4] The following shows the cycle data at 125°C for a molten Na-NaSICON-Na2S3 hybrid flow cell, which is an exemplary embodiment of this technology. [Figure 5] The following shows the cycle data at 125°C for a molten Na-NaSICON-Na2S5 hybrid flow cell, which is an exemplary embodiment of this technology. [Figure 6] The charge and discharge cycle data at 120°C for a molten Na-NaSICON-Na2S5 hybrid flow cell, which is an exemplary embodiment of this technology, are shown. [Figure 7] The charge-discharge curve at 125°C for a molten Na-NaSICON-Na2S2 hybrid flow cell using glycerol as the polar protic solvent for the positive electrolyte, which is an exemplary embodiment of this technology, is shown. [Figure 8] The charge-discharge curve at 125°C for a molten Na-NaSICON-Na2S4 hybrid flow cell using 80 / 20 (mW / mW)EG / NMP as the polar organic solvent for the positive electrolyte, which is an exemplary embodiment of this technology, is shown. [Modes for carrying out the invention]

[0010] Detailed explanation The following terms will be used throughout as defined below.

[0011] Where used herein and in the appended claims, singular articles such as “a,” “an,” and “the,” and similar referents, in the context describing an element (particularly in the context of the appended claims), should be interpreted to encompass both singular and plural forms unless otherwise indicated herein or unless the context clearly contradicts this. Enumerations of ranges of values ​​herein are intended, unless otherwise indicated herein, simply as a simplified way of referring individually to each individual value contained within the range, and each individual value is incorporated herein as if it were individually listed herein. All methods described herein may be carried out in any preferred order unless otherwise indicated herein or unless the context clearly contradicts this. Any and all examples or illustrative language provided herein (e.g., “etc.”) are intended simply to better illustrate embodiments and, unless otherwise stated, do not limit the claims. No language herein should be interpreted as indicating any non-claimed element as essential.

[0012] Where used herein, “about” is to be understood by those skilled in the art and varies to some extent depending on the context in which it is used. Where there is a use of a term that is not obvious to those skilled in the art, “about” means up to plus or minus 10% of the particular term, taking into account the context in which it is used.

[0013] A "sodium ion conductive ceramic film" refers to any suitable ceramic film that prevents the negative electrode active material (e.g., sodium metal) from coming into contact with the positive electrode active material (e.g., sulfur) and catholite, while selectively transporting sodium ions from the negative electrode through the film to the positive electrode, and vice versa.

[0014] As used herein, the term "polar organic solvent" refers to polar protic and polar aprotic organic solvents having a dielectric constant greater than 10. Polar solvents have a large dipole moment established between atoms with very different electronegativities, such as carbon, oxygen, and hydrogen.

[0015] As used herein, the term "polar aprotic solvent" refers to a polar organic solvent that can act as a hydrogen bond acceptor but does not have a hydrogen atom that can act as a hydrogen bond donor. Examples include amides having no hydrogen atom on the amide nitrogen (e.g., dimethylformamide, N-methylpyrrolidone), sulfoxides (e.g., dimethyl sulfoxide), ureas (e.g., N,N'-dimethylpropylene urea), ethers (e.g., tetrahydrofuran, dioxane, diglyme, tetraglyme), carbonates (e.g., dimethyl carbonate, diethyl carbonate), and the like.

[0016] As used herein, the term "polar protic solvent" refers to organic and inorganic solvents that have at least one hydrogen atom bonded to a heteroatom and can participate in hydrogen bonding with a hydrogen bond acceptor. Examples of polar protic solvents include polar protic organic solvents such as alcohols, thiols (e.g., ethylenedithiol), and amides having a hydrogen atom on the amide nitrogen (e.g., primary amides such as formamide and acetamide, secondary amides such as N-methylformamide), as well as polar protic inorganic solvents such as water and ammonia. However, it will be understood by those skilled in the art that for the purposes of the present technology, salts such as ionic liquids are not considered to be polar protic solvents.

[0017] As used herein, the term "alcohol" refers to C having at least one hydroxyl group 1~8 compound. Therefore, in any embodiment, the alcohol has 1, 2, 3, 4, 5, 6, 7, or 8 carbons, or C 1~6 , C 2~8 , C 2~6 , C 2~4The values ​​may be between any two of the aforementioned values ​​and include a range therein. In any embodiment, the alcohol may be polyvalent, having two or three hydroxyl groups, such as glycols (e.g., ethylene glycol, propylene glycol, butane-1,4-diol, diethylene glycol, triethylene glycol, tetraethylene glycol) or triols (e.g., glycerol). However, it will be understood by those skilled in the art that functional groups having multiple oxygen or other heteroatoms, such as carboxylic acid groups or hydroxylamine groups, are not alcohols for use in this art. Furthermore, salts such as ionic liquids are not considered alcohols for use in this art, even if they contain hydroxyl groups.

[0018] In one embodiment, the present technology provides a rechargeable Na-S galvanic cell based on the following cell / battery discharge / charge reaction, in which sodium metal is used as the negative electrode active material and sulfur is used as the positive electrode active material. Positive electrode reaction: TIFF0007926915000002.tif4128 Various orders of polysulfides (e.g., Na2S x In the formula, x is an integer from 1 to 32, and ultimately sulfur is formed at the positive electrode during this conversion. The positive electrode active material may contain a mixture of sodium sulfide and polysulfides as well as sulfur, and the equivalent measured Na2S x It will be understood that the species can include a decimal value of x. For example, an equimolar mixture of Na2S and Na2S2 is Na2S 1.5 It can be measured as follows. Negative electrode reaction: TIFF0007926915000003.tif4128

[0019] The rechargeable galvanic cell is as follows: A negative electrode chamber containing the negative electrode active material, The negative electrode active material contains a liquid alkali metal, and the alkali metal is selected from the group consisting of sodium and sodium alloys, The negative electrode chamber is in fluid communication with the first reservoir so that the liquid alkali metal can flow passively between the negative electrode chamber and the first reservoir when the galvanicellum is being charged or discharged. Negative electrode chamber; A positive electrode chamber containing a mixture of positive electrode active material and positive electrolyte, The positive electrode active material, depending on the charge state of the galvanicellum, contains elemental sulfur and / or Na2S. x The formula includes, where x has values ​​from 1 to 32. The positive electrolyte is Na2S x A polar organic solvent that partially or completely dissolves and The positive electrode chamber is in fluid communication with the pump and the second reservoir so that during charging or discharging of the galvanicellum, the pump can circulate the positive electrode active material and positive electrolyte between the second reservoir and the positive electrode chamber. Positive electrode chamber; and A sodium ion conductive ceramic film separates the negative electrode chamber from the positive electrode chamber. It may include.

[0020] As described above, the negative electrode active material may include a liquid alkali metal, i.e., sodium or a sodium alloy. In any embodiment, the negative electrode active material may include liquid sodium. In any embodiment, the negative electrode active material may include a liquid sodium alloy. It will be understood by those skilled in the art that a suitable sodium alloy consists mainly of sodium metal. In any embodiment, the sodium alloy is at least 80 wt% sodium metal, for example, at least 80 wt%, at least 85 wt%, at least 90 wt%, at least 95 wt%, at least 96 wt%, at least 97 wt%, at least 98 wt%, at least 99 wt%, or a range of sodium metal between and including any two of the aforementioned values. For example, in any embodiment, the sodium alloy may be 80 wt% to 99 wt% sodium metal. Alkali metal alloys may include, for example, alloys having one or more of Si, Ge, Sn, Pb, Hg, Cs, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, and Cd. In any embodiment, the liquid alkali metal may be a sodium alloy containing Cs. In a particular embodiment, if the film is, for example, β''-alumina, the sodium alloy may also contain potassium. The non-sodium metal may be in amounts of 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 8% by weight, 10% by weight, 15% by weight, 20% by weight, or any two of the aforementioned values ​​and amounts containing them.

[0021] During charging or discharging of the galvanicell and battery, the negative electrode active material is in a liquid state at the operating temperature. In any embodiment where the negative electrode active material is sodium, the temperature may be about 100°C to about 200°C, including a range of temperatures between and including any two values ​​selected from, for example, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, and 200°C. If an alloy of sodium metal is used, the temperature used must be the temperature at which the alloy is liquid, for example, about 100°C to about 200°C.

[0022] In any embodiment, the positive electrode active material may include elemental sulfur, alkali metal sulfides, and / or alkali metal polysulfides, depending on the charge state of the galvanicell. For example, the positive electrode active material may include elemental sulfur (S8), sodium sulfide (Na2S), and / or sodium polysulfide (Na2S). x、 In the formula, x may be an integer from 1 to 8, or a higher-order integer from 1 to 32. In any embodiment, the galvanicell is elemental sulfur, as well as / or Na2S, Na2S2, Na2S3, Na2S4, Na2S5, Na2S6, Na2S 16 , and Na2S 32 It may contain one or more of the following. The positive electrode active material can be dissolved or dispersed in a polar organic solvent or solvent mixture to obtain a positive electrolyte.

[0023] The positive electrode active material is generally at least partially soluble in this polar organic solvent, and in solvent mixtures including polar protic organic solvents, optionally accompanied by polar protic inorganic solvents and polar aprotic solvents. In particular, polar protic organic solvents such as alcohols are sodium sulfide (Na2S) and lower-order polysulfide (Na2S) x Although they dissolve at least partially (x=2 or 3), they do not dissolve well in many polar aprotic solvents used in sodium-sulfur batteries at ambient and intermediate temperatures. Higher-order sodium polysulfides also show good solubility, for example, in alcohols and alcohol-containing solvent mixtures in this technology. Therefore, in any embodiment, sodium sulfide and / or polysulfides (e.g., Na2S) x Positive electrolyte solutions (x=2~32) are 0.5M~4M (Na + It can be prepared based on, for example, 0.5 or 1-3 M, or 2-3 M concentrations.

[0024] Depending on the charge or discharge state of the cell, the positive electrode active material Na2S xThe composition can vary, and phase separation may occur because the solubility differs across the compositional range of Na2S, various polysulfides, and elemental sulfur. In any embodiment, the polar organic solvent includes a polar protic solvent or a mixture thereof. To improve the solubility of Na2S, a mixture of a polar protic solvent, such as an alcohol, and another polar protic solvent may be used. For example, an ethylene glycol-water mixture may be used to dissolve more Na2S than pure ethylene glycol. Thus, in any embodiment, the positive electrolyte may be a mixture of two or more polar protic solvents, such as an alcohol mixed with another polar protic solvent. To improve solubility with elemental sulfur, the positive electrolyte in this art may also include a polar aprotic solvent.

[0025] The ability of polar protic solvents to dissolve compositions ranging from Na2S to Na2S2, and even higher-order polysulfides up to Na2S6, and to at least partially dissolve even higher-order polysulfides or even sulfur (with the addition of polar aprotic solvents) in the temperature range of 100-200°C, offers several advantages. Firstly, it increases the available cathode capacity to over 80% of the theoretical sulfur cathode capacity (i.e., over 80% of 1675 mAh / g). Secondly, the high sulfide / polysulfide solubility of the positive electrolyte of the present invention allows for high Na2S / polysulfide solubility in the range of 30-60 mS / cm. + This leads to ionic conductivity (Figure 2), supporting high charge and discharge currents in this galvanic cell. Furthermore, protic solvents are often less expensive than their aprotic counterparts.

[0026] In any embodiment, the polar protic organic solvent may be selected from the group consisting of alcohols, thiols, primary amides, and secondary amides, and any two or more mixtures thereof. In any embodiment, the polar protic organic solvent may be an alcohol, a mixture of two or more alcohols, or a mixture of one or more alcohols with another polar protic and / or aprotic solvent. The polar organic solvent or mixture of solvents (including any polar protic solvent) is selected to remain in the liquid phase over the operating temperature of the galvanicellus, for example, about 100°C to about 200°C (or a subset thereof). Therefore, in any embodiment, the organic solvent (including polar protic solvents) may be selected to remain liquid over an operating temperature range of about 100°C to about 180°C, or about 110°C to about 150°C, about 100°C to about 125°C, about 100°C to about 150°C, 125°C to about 150°C, about 125°C to about 175°C, about 125°C to about 200°C, or about 150°C to about 200°C. Suitable polar protic organic solvents that are liquids within one or more of the specified temperature ranges include alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, dihydroxybenzyl alcohol (e.g., 3,5-dihydroxybenzyl alcohol, 3,4-dihydroxybenzyl alcohol, or 2,4-dihydroxybenzyl alcohol), cyclopentane-1,2-diol, cyclopentane-1,3-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, diethylene glycol, triethylene glycol, and tetraethylene glycol.

[0027] In any embodiment of this rechargeable galvanic cell, the positive electrolyte may include one or more polar aprotic solvents such as alcohols or thiols (including dithiols), optionally a carboxylic acid, ammonia, water, or any two or more combinations thereof. In any embodiment, the positive electrolyte may include alcohols such as ethylene glycol, propylene glycol, glycerol, cyclohexanediol, or any two or more combinations thereof. The positive electrolyte may further include water. Depending on the charging or discharging state of the cell, the positive electrode active material may be Na2S x The composition changes, and phase separation can occur because the solubility differs within the compositional range of Na2S, polysulfides, and elemental sulfur. To improve the solubility of Na2S, a mixture of alcohol and water or a polar protic solvent, for example, a mixture of ethylene glycol and water, may be used. Similarly, a mixture of alcohol and a polar protic solvent and / or a polar aprotic solvent may be used to dissolve higher-order polysulfides (e.g., Na2S6, Na2S7, Na2S8, ..., Na2S 32 ) and S8 can be used to improve solubility. For example, an ethylene glycol / N-methyl-2-pyrrolidone (NMP) mixture can be used to dissolve more polysulfides than ethylene glycol alone. In this manner, the entire theoretical capacity of elemental sulfur from Na2S can be realized in this galvanicell. Nevertheless, as will be further described herein, it will be understood that the mixture of the positive electrode active material and the positive electrolyte can also be a mixture of one or more solid phases and one or more liquid phases.

[0028] In any embodiment, the polar organic solvent may be a mixture of a polar protic solvent and / or a polar aprotic solvent, and may also contain small amounts (less than 20% by weight, less than 10% by weight, less than 5% by weight) of water or other protic solvents such as carboxylic acids. In any embodiment, the positive electrolyte may contain a larger amount of polar protic solvent mixed with an optional smaller amount of polar aprotic solvent. In any embodiment, the positive electrolyte may contain a larger amount of alcohol mixed with an optional different polar protic solvent and an optional smaller amount of polar aprotic solvent. In any embodiment, the positive electrolyte may include more than 50% by weight of a polar protic solvent and less than 50% by weight of a polar aprotic solvent, such as 51 / 49% by weight, 55 / 45% by weight, 60 / 40% by weight, 70 / 30% by weight, 80 / 20% by weight, 90 / 10% by weight, 95 / 5% by weight, and 99 / 1% by weight of a polar protic solvent versus a polar aprotic solvent, or a range between any two of the aforementioned ratios and including them. In any embodiment, the positive electrolyte may include more than 50% by weight of alcohol, a mixture of alcohols, or a mixture of alcohol and another polar protic solvent, and less than 50% by weight of a polar aprotic solvent, such as 51 / 49% by weight, 55 / 45% by weight, 60 / 40% by weight, 70 / 30% by weight, 80 / 20% by weight, 90 / 10% by weight, 95 / 5% by weight, and 99 / 1% by weight of alcohol / polar protic solvent versus polar aprotic solvent, or a range between any two of the aforementioned ratios and including them. Examples of aprotic solvents that may be used include at least one of N,N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), dimethyl carbonate, diethyl carbonate, dioxane, dimethyl ether, tetraglyceride, and diglyme. In any embodiment, the positive electrolyte may include an alcohol (e.g., ethylene glycol or any of those described herein) having 2% to 20% by weight of a polar protic solvent other than alcohol (e.g., water, acetic acid, acetamide, and 1,3-propanedithiol).For example, the positive electrolyte may comprise 2, 4, 6, 8, 10, 12, 14, 16, 18, or 20% by weight of a non-alcohol polar protic solvent, or a range between any two of the aforementioned values ​​and including them. In any embodiment, the positive electrolyte may comprise 1 to 40% by weight of a polar aprotic solvent (e.g., NMP or any of those described herein), for example, 1, 2, 5, 10, 15, 20, 25, 30, 35, or 40% by weight of a polar aprotic solvent, or a range between any two of the aforementioned values ​​and including them. In any embodiment, the electrolyte comprises an alcohol, a non-alcohol polar protic solvent, and a polar aprotic solvent in any of the amounts described herein. In any embodiment, the positive electrolyte may comprise 40 to 96% ethylene glycol, 0 to 20% by weight of water, and 1 to 40% by weight of NMP. The positive electrolyte may also include non-sodium salts such as ammonium hydroxide and tetramethylammonium hydroxide. However, in any embodiment, the positive electrolyte may exclude non-sodium salts.

[0029] In any embodiment, additional sulfur / polysulfide / sodium sulfide beyond their solubility limits may be present to increase the capacity of the galvanicellate, providing a semi-solid mixture of soluble / unsoluble positive electrode active material and a polar organic solvent (e.g., alcohol and any other solvent described herein). If the positive electrolyte is semi-solid, it will be understood to be a fluid semi-solid. In any embodiment, the positive electrolyte may contain more than 0% by weight and up to 50% by weight of unsoluble positive electrode active material, i.e., sulfur and / or sodium polysulfide and / or sodium sulfide. In any such embodiment, the amount of unsoluble positive electrode active material includes more than 0% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight, 40% by weight, or more than 50% by weight, or a range between any two of the aforementioned values ​​and including them, e.g., more than 0% by weight and up to 40% by weight, more than 0% by weight and up to 30% by weight, or 1% by weight and up to 20% by weight.

[0030] The rechargeable galvanic cell of this technology may further include a ceramic film, a negative electrode active material, and / or a heat source and / or cooling source for maintaining the temperature of the positive electrode active material and positive electrolyte. If the negative electrode active material is sodium, the heat source and / or cooling source maintains a temperature of about 100°C to about 200°C. For example, the heat source and / or cooling source may be one or more heat exchangers that are in fluid and / or thermal communication with the positive electrode chamber and heat and / or cool the positive electrolyte to a temperature of about 100°C to about 200°C before it enters the positive electrode chamber.

[0031] In this rechargeable galvanic cell, the sodium ion-conducting ceramic film separates the negative electrode active material from the positive electrode active material. In any embodiment, the sodium ion-conducting ceramic film may be a sodium superionic conductor (NaSICON), a sodium ion-conducting garnet-like ceramic, a sodium β''-alumina film, or a sodium-conducting glass ceramic. The NaSICON composition is Na3Zr2Si2PO 12 kaNa 1+x Si x Zr2P 3-x O 12 (In the formula, x = 1.6 to 2.4), yttrium-doped NaSICON (for example, Na 1+x+y Zr 2-y Y y Si x P 3-x O 12 kaNa 1+x Zr 2-y Y y Si x P 3-x O 12-y (In the equation, x = 1.6 to 2.4, y = 0 to 0.25), Na 1+x Zr2X y (PO4)3, where x is 0 to 3, y is 0 to 1.5, X is a dopant (e.g., Fe, Al, Ti, Hf, Co, Ni, Nb), and Fe-doped NaSICON (Na3Zr 2 / 3 Fe 4 / 3 P3O 12Examples of Na-β''-alumina films include, but are not limited to, Na (1.53~1.73) Li (0.28~0.32) Al (10.66~10.72) O 17 In any embodiment, the sodium ion conductive ceramic film is A x B2C3O 12 (In the formula, A is an alkali metal ion, and x = 3 to 9, (B = Te 6+ Ta 5+ Nb 5+ , Zr 4+ , C=La 3+ , Y 3+ , Nd 3+ It may be a sodium ion conductive garnet-like ceramic having the general formula ). Non-limiting examples of Na conductive ceramic glass include sodium phosphate such as xNa2O.yP2O5, sodium silicate such as xNa2O.ySiO2, sodium borate such as xNa2O.yB2O3, sodium aluminate such as xNa2O.yAl2O3, and any two or more mixtures thereof, in any of the above, the molar ratio of x:y may be in the range of 1:3~3:1, 1:2~3:1, 1:2~2:1, 1:2~1:1, 1:3~2:1, or 1:3~1:1.

[0032] In any embodiment, the rechargeable galvanicellum may further include a positive electrode current collector positioned within the positive electrode chamber. The positive electrode current collector is configured to ensure electrical contact with the positive electrolyte regardless of how the positive electrode active material changes within the positive electrolyte. In other words, the positive electrode current collector is electrically connected to the liquid (dissolved) or solid (undissolved) positive electrode active material and the polar protic solvent, regardless of the physical changes in the mixture. The positive electrode current collector may include nickel foam, nickel mesh, carbon foam, or carbon felt.

[0033] For example, to improve the electrical conductivity of the positive electrode, electrical conductors such as carbon particles may be used by including carbon particles in the positive electrolyte. Similarly, ionic conductivity enhancers may be advantageously added to positive electrolytes lacking significant sodium ionic conductivity to improve conductivity and increase current density. In any embodiment, a rechargeable galvanic cell may include a conductivity enhancer selected from the group consisting of sodium halides (e.g., NaCl, NaBr, and NaI), sodium carboxylates (e.g., sodium formate, sodium acetate), sodium sulfur oxygenates (e.g., Na2SO4, Na2SO3, Na2S2O3), sodium hydrosulfide (NaSH), sodium hydroxide, sodium cyanate, sodium carbonate (e.g., sodium carbonate, sodium bicarbonate), and any two or more combinations thereof. Examples of suitable conductivity enhancers include NaI, NaOH, HCOONa, CH3COONa, Na2CO3, NaOCN, Na2SO4, and any two or more combinations thereof. In any embodiment, the positive electrolyte comprises carbon particles that can form a semi-solid suspension using an alcohol or an alcohol solvent mixture. In any embodiment, 0.01% to 20% by weight of a sodium conductivity enhancer may be present in the positive electrolyte. For example, the positive electrolyte may contain 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.5% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 8% by weight, 10% by weight, 12% by weight, 15% by weight, 16% by weight, 18% by weight, and 20% by weight of a sodium ion conductivity enhancer, or a range of sodium ion conductivity enhancers between any two of the aforementioned values ​​and including them. Therefore, for example, the positive electrolyte may optionally contain 0.1% to 20% by weight, 1% to 18% by weight, or 5% to 15% by weight of a sodium ion conductivity enhancer. A conductivity improvement of at least 10% to 100% can be obtained using a positive electrolyte containing such an improver, compared to the same electrolyte without such an improver.In some embodiments, the improvement is at least 10%, at least 20%, at least 40%, at least 60%, at least 80%, at least 100%, or a range between and including any two of the aforementioned values.

[0034] The cell design may include an active circulation option for the positive electrolyte to improve cathode performance. This type of positive electrolyte-only flow provides a hybrid flow battery, in contrast to flow batteries in which both positive and negative electrolytes circulate (as mentioned in the literature). Figure 1 shows one possible configuration of the hybrid flow battery architecture of this technology.

[0035] A reservoir (e.g., a tank) may be provided to hold the majority of the positive electrolyte. A recirculation pump may be used to circulate the positive electrolyte through the cell. More specifically, the positive electrolyte can flow through the inlet into the positive electrode chamber, and exit through the outlet, for example, through the pores of a Ni foam current collector. Thus, the positive electrolyte brings the positive electrode material into contact with the current collector, where they can undergo electrochemical charge / discharge reactions. It should be understood that the design of the positive electrode chamber is expected to vary as needed, based on the type of (liquid or semi-solid) positive electrode active material and positive electrolyte being used.

[0036] Another design feature may be that the molten sodium in the negative electrode chamber is fluidly connected (e.g., via a conduit) to a separate tank (overflow reservoir) containing a pool of sodium such that only a small amount can be present in the negative electrode chamber. Housing the negative electrode in a separate tank from the cell may be advantageous because it can reduce the size of the battery. The sodium overflow reservoir receives excess sodium during charging of the hybrid battery and supplies it to the battery during discharging. Alternatively, the battery may be a "stagnation" system where the molten sodium remains in the electrode chamber, for example, under an inert gas.

[0037] It should be noted that the cell may be contained within a temperature-controlled environment to ensure it operates at an appropriate temperature. In some embodiments, this temperature may be between 100°C and 200°C.

[0038] In one embodiment, the cell operates at a high temperature (charging and discharging) while the positive electrolyte tank is kept at a lower temperature. In this case, a heat generator or heat exchanger may be used to heat the cell to the desired high temperature.

[0039] In any embodiment, the rechargeable galvanicell, the first reservoir, and the second reservoir may be sized to hold enough electrode active material for discharge operation of the cell for about 1, 2, 5, 10, 20, or 50 hours, or between any two of the aforementioned values ​​and in a range including those.

[0040] In another embodiment, the Art provides a battery comprising one or more (e.g., two or more) galvanic cells as described herein. For example, in any embodiment, a battery may comprise 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 40, 50, 60, 80, 100, 150, 200, 250, 300, 350, 400, 450, or 500 galvanic cells as described herein, or a range between and including any two or more of the aforementioned values, e.g., 1 to 500, 2 to 200, or 50 to 350 galvanic cells. Two or more batteries (each comprising two or more galvanic cells) may be used together to manufacture a battery storage system. For example, a 350 kW battery may comprise 320 individual cells, and a battery system designed to provide a 2 MW output may comprise 50 such batteries, each having 12,800 individual cells. Therefore, in any embodiment, the technology provides a battery system comprising two or more batteries, each containing two or more cells.

[0041] In another embodiment, this technology is, The galvanicell is charged or discharged while circulating a mixture of the positive electrolyte and positive electrode active material from the second reservoir back to the second reservoir through the positive electrode chamber. Before or when the mixture enters the positive electrode chamber, the mixture is heated to a first temperature of approximately 100°C to approximately 200°C. After the mixture leaves the positive electrode chamber, the mixture is cooled to a second temperature lower than the first temperature, for example, below 100°C. This specification provides a method for operating the rechargeable galvanicellum described herein, including [specific details omitted].

[0042] In any embodiment in which the mixture of the positive electrolyte and the positive electrode active material is heated to a temperature above 100°C before or when it enters the positive electrode chamber, the mixture may then be cooled to a temperature below the same temperature when it exits the positive electrode chamber. For example, if the mixture of the positive electrolyte and the positive electrode active material is heated to a temperature of 115°C to 150°C, 175°C, or 200°C, or 120°C to 150°C, 175°C, or 200°C, or 125°C to 150°C, 175°C, or 200°C, the mixture may then be cooled to a minimum temperature, i.e., below 115°C, 120°C, or 125°C. In some such embodiments, the temperature range in which the mixture is cooled is 80°C to less than 115°C, 120°C, or 125°C; 90°C to less than 115°C, 120°C, or 125°C; or 100°C to less than 115°C, 120°C, or 125°C. In any embodiment, the method includes heating (or cooling) the mixture to a temperature of about 125°C to about 175°C. In any embodiment, the method includes heating (or cooling) the mixture to a temperature of about 125°C to about 150°C. In any embodiment, the method may include cooling (or heating) the mixture after it has left the cathode chamber to a temperature of about 80°C to less than 100°C.

[0043] An exemplary embodiment of the present technology is described with reference to Figure 1A, which schematically shows a rechargeable alkali metal-sulfur hybrid flow cell 100. The cell includes a negative electrode 110 containing a negative electrode active material (e.g., sodium or an alloy thereof) located in a negative electrode chamber 115. The cell also includes a positive electrode 120 containing a positive electrode active material, located in a positive electrolyte 125 containing the positive electrode active material. An alkali ion-conducting ceramic membrane 130 (e.g., NaSICON, Na-β''-alumina, sodium ion-conducting garnet-like ceramic, sodium-conducting glass ceramic) separates the negative electrode chamber and the positive electrode chamber, as well as their contents. The membrane 130 may be secured to the cell housing using O-rings 140A and 140B. The cell may include negative and positive current collectors 150A and 150B, respectively, which are in electrical contact with the negative and positive electrodes. The mixture of the positive electrolyte and the positive electrode active material is stored in a reservoir 170, which is in fluid communication with both the pump 160 and the positive electrode chamber 125. During cell operation, the mixture of the positive electrolyte and the positive electrode active material is circulated inside and outside the positive electrode chamber by the pump. Optional heat exchangers for controlling the temperature of the mixture, as well as passive alkali metal reservoirs fluidly connected to the negative electrode chamber for storing excess alkali metals, are not shown. A sodium-sulfur version of this cell was used in the following experiments.

[0044] Any of the galvanic cells described herein, for example, the embodiment shown in Figure 1A, can be incorporated into a variety of systems and processes. As an exemplary embodiment only, the process flow diagram (PFD) shown in Figure 1B illustrates one possible system 200 for performing the charging and discharging processes of the present art. Sulfur and sodium salts 205—for example, sodium sulfide and polysulfides—are added as needed to a positive electrolyte tank (reservoir) 210 containing an alcohol, for example, an alkyldiol as described herein, such as ethylene glycol or propylene glycol, but not limited to these. The positive electrolyte 212 is pumped from the positive electrolyte tank 210 to a splitter 220 via a fluid drive device 215 (e.g., a pump), where portion 225 is then led to a filter 230 for filtering out any undissolved solids. Next, the filtered positive electrolyte 232 is led to a heat exchanger 235, where it is heated to a temperature above 120°C, for example, about 125°C to about 150°C, as described herein. The heated fluid is introduced into (236A) and discharged (236B) from the heat exchanger to maintain an appropriate temperature. The heated positive electrolyte 234 is introduced into the positive electrode chamber of a galvanic cell or a series of cells 240 (see, for example, Figure 1A), where sodium ions are generated (during discharge) or sodium metal 245 is regenerated from sodium ions (during charging) and then removed from the cell. Once out of the galvanic cell, the positive electrolyte 242 is cooled in a second heat exchanger 250 to a temperature below 110°C, for example, about 80°C to about 100°C, as described herein. The cooled positive electrolyte 255, which may contain some dissolved elemental sulfur (depending on the cell state), is recirculated to a positive electrolyte tank 210.

[0045] Optionally, in the splitter 220, a portion of the anolite 260 coming out of the anolite tank is sent to the crystallizer 265, where the anolite is cooled to a temperature of approximately 15°C to 80°C by a cooling fluid circulating inside (266A) and outside (266B) the crystallizer. Other suitable temperatures within this range may be used, for example, including 15°C to 60°C, 30°C to 80°C, or 40°C to 80°C. Sulfur 277 precipitates, including crystals, and is then filtered as the anolite 270 passes through the sulfur filter 275. If the temperature of this part of the system and process is too low, the solubility of sulfur in the anolite decreases, leading not only to the precipitation / crystallization of sulfur (S8) but also to Na2S x This destabilizes the sulfur and also promotes the formation and precipitation / crystallization of S8. The desulfurized anorite 280 is then returned to the anorite tank 210 for recirculation. It will be understood by those skilled in the art that other methods for removing dissolved sulfur from anorite 260 may be used, such as gravimetric methods (e.g., centrifugation). Alternatively, different anorite solvent systems with lower sulfur solubility may be used at temperatures above the melting point of sulfur, so that elemental sulfur can be removed as a liquid. Furthermore, other sulfur removal techniques, such as extraction using a nonpolar solvent that is immiscible with anorite, may be used. It is within the scope of the art to modify this system and process to use any suitable sulfur removal technique and to make other minor changes, such as adding additional fluid drives (e.g., pumps), filters, heat exchangers, etc., as needed, and to arrange such components to suit the needs at hand. [Examples]

[0046] Example 1 - Na2S in ethylene glycol x conductivity Different amounts and types of Na2S in ethylene glycol (Univar) xThe ionic conductivity of the electrolyte was measured using a standard method with an AST52 conductive probe (Advanced Sensor Technologies, Inc.). The concentration of the polysulfide was expressed as sodium weight % in the mixture. The results are shown in Figure 2. Conductivity decreased as the number of sulfur atoms in the polysulfide increased.

[0047] Example 2 - Initial charge and discharge cycles of sodium-sulfur galvanicellates using Na2S Figure 3 shows a positive electrode using molten sodium as the negative electrode, a 1 mm thick NaSICON ceramic film, ethylene glycol as the polar protic solvent for a positive electrolyte containing 10 wt% Na2S (approximately 6 wt% Na) as the positive electrode active material, and nickel foam as the positive electrode current collector, with a film thickness of 1 cm². 2 At 100 mA per unit, this represents the first charge and discharge cycle at 125°C of a cell as described herein, i.e., the cell in Figure 1A. During the cycle, the composition of the positive electrode active material is measured by atomic absorption using a Perkin Elmer AAnalyst 200 spectrometer, or by ICP (sodium), X-ray fluorescence, or ICP (sulfur). The image transitioned left and right between TIFF0007926915000004.tif4128.

[0048] Example 3 - Charging and discharging cycles of sodium-sulfur galvanicellals using Na2S3 Figure 4 shows a positive electrode using molten sodium as the negative electrode, a 1 mm thick NaSICON ceramic film, ethylene glycol as the polar protic solvent for the positive electrolyte containing 12.5 wt% Na2S3 (approximately 4 wt% Na) as the positive electrode active material, and nickel foam as the positive electrode current collector, with a film thickness of 1 cm². 2 This shows the charge and discharge cycle performance of the cell at 125°C with a current of 100mA per cycle. During the cycle, the composition of the positive electrode active material is The image transitioned left and right between TIFF0007926915000005.tif4128.

[0049] Example 4 - Charging and discharging cycles of sodium-sulfur galvanicellals using Na2S5 Figure 5 shows the charge and discharge cycle performance of a cell at 125°C at 100 mA per square cm of film, using molten sodium as the negative electrode, a 1 mm thick NaSICON ceramic film, ethylene glycol as the polar protic solvent for a positive electrolyte containing 18 wt% Na2S5 (approximately 4 wt% Na) as the positive electrode active material, and nickel foam as the positive electrode current collector. During the cycle, the composition of the positive electrode active material changes. The image transitioned from left to right between TIFF0007926915000006.tif4128.

[0050] Figure 6 shows the charge and discharge cycle performance of a cell at 120°C at 50 mA per square cm of film, using molten sodium as the negative electrode, a 1 mm thick NaSICON ceramic film, ethylene glycol as the polar protic solvent for a positive electrolyte containing 9.7 wt% Na2S5 (approximately 2.3 wt% Na) as the positive electrode active material, and carbon cloth as the positive electrode current collector. During the cycle, the composition of the positive electrode active material changes. The transition occurred between TIFF0007926915000007.tif4128. The result was that Na2S in this galvanicellate x This shows the high-capacity window of the cathode (1061mAh / g).

[0051] Example 5 - Initial charge and discharge cycles of a sodium-sulfur galvanic cell using Na2S2 A galvanicell was constructed in the same manner as in Example 2, but glycerol was used as the polar protic solvent for the positive electrolyte, 5% Na2S2 as the positive electrode material, molten sodium as the negative electrode, and a 1 mm thick NaSICON ceramic film was used. During the cycle, the composition of the positive electrode active material was as follows: The image transitioned left and right between TIFF0007926915000008.tif4128. Figure 7 shows the 1cm interval. 2This represents a first charge and discharge cycle at 125°C for a cell as described herein, with a current of 50 mA per unit. In a second embodiment, the same cell is operated at a temperature of 150–175°C to improve current-voltage performance.

[0052] Example 6 - Initial charge and discharge cycles of a sodium-sulfur galvanic cell using Na2S2 The cell was constructed similarly to Example 2, but an 80%:20% (weight / weight) mixture of ethylene glycol and NMP was used as the polar organic solvent for the positive electrolyte (a mixture of polar protic and polar aprotic solvents), and 5% Na2S4 was used as the cathode material. Na2S4<->Na2S 4.77 Figure 8 shows the charge-discharge data for the transition between left and right. The presence of NMP, a polar aprotic solvent, leads to the formation of higher-order polysulfides (Na2S4, Na2S5, ...Na2S 32 It facilitates the solubilization of , and S), and helps extend the volume range to include sulfur.

[0053] Example 7 - Initial charge and discharge cycles of sodium-sulfur galvanicellates using Na2S2 The cell is constructed similarly to Example 2, but a β''-alumina film of the same thickness as the NaSICON ceramic film is used to separate the negative electrode chamber from the positive electrode chamber. Due to the lower conductivity of the β''-alumina film, the cell has a current density of 33 mA / cm² in the corresponding NaSICON test (Figure 3). 2 It is expected to operate at one-third of the value of the first embodiment. In the second embodiment, a thinner β''-alumina film is used to provide a higher current density than in the first embodiment.

[0054] Equal parts While specific embodiments are illustrated and described, those skilled in the art can, after reading the foregoing specification, make changes, substitutions of equivalents, and other kinds of modifications to the PDCs or their derivatives, prodrugs, or these pharmaceutical compositions described herein. Each of the embodiments described above may also include, or be incorporated with, any or all of the other embodiments and embodiments disclosed herein.

[0055] This technology should not be limited to any particular embodiment described herein, but is intended as a single example of individual embodiments of this technology. As will be apparent to those skilled in the art, many modifications and variations of this technology can be made without departing from its spirit and scope. Functionally equivalent methods within the scope of this technology, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to be within the scope of the appended claims. It should be understood that this technology is not limited to any particular method, conjugate, reagent, compound, composition, labeled compound, or biological system, and these can, of course, be changed. All methods described herein may be carried out in any preferred order unless otherwise indicated herein or unless it is clearly inconsistent with the context. It should also be understood that the terms used herein are intended to describe only particular embodiments and are not intended to be limiting. Accordingly, this specification is intended to be considered only as an example of the breadth, scope, and spirit of this technology as shown only by the appended claims, the definitions therein, and any equivalents thereof. No language in this specification should be construed as indicating any non-claimed element as essential.

[0056] Embodiments described herein exemplary may also be suitably implemented without elements or limitations not specifically disclosed herein. Therefore, terms such as “comprising,” “including,” and “containing” should be read broadly and without limitation. Furthermore, the terms and expressions used herein are described, not limited, and in the use of such terms and expressions, there is no intention to exclude any equivalents of the shown and described features or any part thereof, but it should be recognized that various modifications are possible within the scope of the claimed technology. In addition, the phrase “essentially consisting of” should be understood to include the specifically enumerated elements and any additional elements that do not substantially affect the fundamental and novel characteristics of the claimed technology. The phrase “consisting of” excludes any elements not specified. Furthermore, the use of any of the aforementioned terms in a description relating to a particular element or embodiment also intends to include the use of any of the other terms. For example, the use of “including” relating to one element or embodiment should also be understood to disclose the use of “essentially consisting of” or “consisting of” relating to the same element or embodiment, and vice versa.

[0057] In addition, where any feature or aspect of the present disclosure is described in relation to the Markush group, a person skilled in the art will recognize that the present disclosure also describes any individual member or subgroup of a member of the Markush group. Each of the narrower groups of species and subgenera included in the general disclosure also forms part of the art. This includes general descriptions of the art that have provisos or negative limitations that remove any subject matter from a genus, whether or not the excluded material is specifically enumerated herein.

[0058] As will be understood by those skilled in the art, for any and all purposes, and especially in terms of providing written descriptions, all scopes disclosed herein also encompass any and all possible sub-scopes and combinations thereof. Any scopes listed arbitrarily may be readily recognized as sufficiently described and enabling the same scope to be divided into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each scope considered herein may readily be divided into lower thirds, middle thirds, upper thirds, etc. As will also be understood by those skilled in the art, all language such as “maximum,” “at least,” “greater than,” and “less than” includes the number listed and refers to a scope that can subsequently be divided into sub-scopes as considered above. Finally, as will be understood by those skilled in the art, a scope includes each individual member, and each distinct value is incorporated herein as if it were individually listed herein.

[0059] All patent publications, patent applications, issued patents, and other documents (e.g., journals, articles, and / or textbooks) referenced herein are incorporated by reference as if each individual patent publication, patent application, issued patent, or other document, in whole, were specifically and individually indicated to be incorporated by reference. Definitions contained in textbooks incorporated by reference are excluded to the extent that they conflict with the definitions in this disclosure.

[0060] Other embodiments are described in the appended claims, along with the entire scope of equivalents to which such claims are entitled.

Claims

1. It is a rechargeable galvanic cell, and the following: A negative electrode chamber containing the negative electrode active material, The negative electrode active material includes a liquid alkali metal selected from the group consisting of molten sodium and molten sodium alloys, and The negative electrode chamber is in passive fluid communication with the first reservoir via a conduit, so that the liquid alkali metal can flow passively between the negative electrode chamber and the first reservoir when the galvanicellum is being charged or discharged. Negative electrode chamber; A positive electrode chamber containing a positive electrolyte comprising a mixture of a positive electrode active material, a solvent, and a conductivity enhancer in an amount of about 0.01% to about 20% by weight, The positive electrode active material contains elemental sulfur and / or Na depending on the charge state of the galvanicellum. ２ S ｘ The formula includes, where x has values ​​from 1 to 8, The solvent is the Na ２ S ｘ A polar organic solvent containing a polar protic organic solvent that partially or completely dissolves the substance, The conductivity improving agent comprises a mixture of sodium carboxylate and sodium sulfur oxygeneate, During charging or discharging of the galvanicellum, the positive electrode chamber is in fluid communication with the pump and the second reservoir so that the pump can circulate the positive electrode active material and positive electrolyte between the second reservoir and the positive electrode chamber. Positive electrode chamber; and A sodium ion conductive ceramic film separating the negative electrode chamber from the positive electrode chamber; and A heat source for maintaining the temperature of the rechargeable galvanic cell at approximately 100°C to 200°C. Includes a rechargeable galvanic cell.

2. The rechargeable galvanic cell according to claim 1, wherein the negative electrode active material is molten sodium.

3. The aforementioned heat source, A heat exchanger that is in fluid communication with the positive electrode chamber and heats the positive electrolyte to a temperature of approximately 100°C to approximately 200°C before the positive electrolyte enters the positive electrode chamber. The rechargeable galvanic cell according to claim 1.

4. The rechargeable galvanicelled according to claim 1 or 2, wherein the sodium ion conductive ceramic film comprises at least one of NaSICON, sodium ion conductive garnet-like ceramic, sodium β''-alumina, and sodium conductive glass ceramic.

5. The rechargeable galvanic cell according to any one of claims 1 to 4, wherein the positive electrolyte has a conductivity of at least 30 mS / cm at a temperature of 100°C to 200°C.

6. The rechargeable galvanicellent according to claim 1, wherein the polar protic organic solvent is selected from the group consisting of alcohols, thiols, primary amides, and secondary amides, and any two or more mixtures thereof.

7. The rechargeable galvanicellent according to any one of claims 1 to 6, wherein the polar organic solvent comprises one or more of 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, dihydroxybenzyl alcohol, cyclopentane-1,2-diol, cyclopentane-1,3-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol.

8. The aforementioned polar organic solvent Alcohol and, A solvent selected from the group consisting of water, acetic acid, acetamide, ammonium hydroxide, tetramethylammonium hydroxide, and 1,3-propanedithiol. including A rechargeable galvanic cell according to any one of claims 1 to 6.

9. The rechargeable galvanic cell according to any one of claims 1 to 8, wherein the positive electrolyte comprises a polar protic solvent containing an alcohol and a polar aprotic solvent, the polar aprotic solvent comprising at least one of dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl carbonate, diethyl carbonate, tetraglyceride, and diglyme, and the positive electrolyte comprises more than 50% by weight of the polar protic solvent and less than 50% by weight of the polar aprotic solvent.

10. The rechargeable galvanicelled cell according to any one of claims 1 to 8, wherein the positive electrolyte comprises 40 to 96% ethylene glycol, 0 to 20% by weight of water, and 1 to 40% by weight of NMP.

11. A positive electrode current collector is disposed within the positive electrode chamber and electrically connected to the positive electrode active material. The rechargeable galvanic cell according to any one of claims 1 to 8, further comprising, wherein the positive electrode current collector comprises nickel foam, nickel mesh, carbon foam, or carbon felt.

12. The conductivity improver is CH ３ COONa, Na ２ CO ３ , Na ２ SO ４ , Na ２ SO ３ , and Na ２ S ２ O ３ The rechargeable galvanic cell according to any one of claims 1 to 11, which is selected from the group consisting of:

13. The rechargeable galvanic cell according to any one of claims 1 to 12, wherein the first reservoir and the second reservoir are sized to hold sufficient electrode active material for 1 to 50 hours of discharge operation of the cell.

14. The rechargeable galvanicelled cell according to claim 7 or 8, wherein the polar organic solvent comprises ethylene glycol.

15. A rechargeable battery comprising one or more rechargeable galvanic cells as described in any one of claims 1 to 14.

16. A method for operating a rechargeable galvanicell, A negative electrode chamber containing the negative electrode active material, The negative electrode active material includes a liquid alkali metal selected from the group consisting of molten sodium and molten sodium alloys, and The negative electrode chamber is in passive fluid communication with the first reservoir via a conduit, so that the liquid alkali metal can flow passively between the negative electrode chamber and the first reservoir when the galvanicellum is being charged or discharged. Negative electrode chamber; and A positive electrode chamber containing a positive electrolyte comprising a mixture of a positive electrode active material, a solvent, and a conductivity enhancer in an amount of about 0.01% to about 20% by weight, The positive electrode active material, depending on the charge state of the galvanic cell, Na ２ S ｘ The formula includes, where x has values ​​from 1 to 8, The solvent is the Na ２ S ｘ A polar organic solvent containing a polar protic solvent that partially or completely dissolves the substance, The conductivity improving agent comprises a mixture of sodium carboxylate and oxygen-containing sodium sulfur. Positive electrode chamber Includes, The negative electrode chamber and the positive electrode chamber are separated by a sodium ion conductive ceramic film. To provide a rechargeable galvanic cell, The positive electrolyte is heated to a temperature of approximately 100°C to approximately 200°C before or when it enters the positive electrode chamber. Maintaining the temperature of the ceramic film, the negative electrode active material, and / or the positive electrolyte at a temperature of approximately 100°C to approximately 130°C, The galvanicell is charged or discharged while the mixture of the positive electrolyte and the positive electrode active material is circulated from the second reservoir through the positive electrode chamber back to the second reservoir. Methods that include...

17. The method according to claim 16, comprising heating the mixture to a temperature of 100°C to 150°C or 110°C to 150°C, and / or cooling the mixture to a temperature of 80°C to less than 100°C or less than 115°C after the mixture has left the positive electrode chamber.

18. (a) The polar organic solvent comprises one or more of the following: 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, dihydroxybenzyl alcohol, cyclopentane-1,2-diol, cyclopentane-1,3-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; and / or (b) The polar protic solvent is selected from the group consisting of alcohols, thiols, primary amides, and secondary amides, and any two or more mixtures thereof. The method according to claim 16.

19. The method according to any one of claims 16 to 18, wherein the positive electrolyte comprises 40 to 96% ethylene glycol, 0 to 20% by weight of water, and 1 to 40% by weight of NMP.

20. The aforementioned conductivity improving agent is CH ３ COONa, Na ２ CO ３ Na ２ SO ４ Na ２ SO ３ , and Na ２ S ２ O ３ A method according to any one of claims 16 to 19, selected from the group consisting of the following.

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