A dual electrolyte method for increasing the energy density of metal-based batteries.

Abstract

The goal is to enable high energy density. The dual electrolyte battery includes a cathode, an anode, a catholyte in contact with the cathode, and an anolyte in contact with the anode. The catholyte includes a first gelled electrolyte, and the anolyte includes a second gelled electrolyte. The concentration of the electrolyte in the anolyte is greater than the concentration of the electrolyte in the catholyte.

Description

[Technical Field]

[0001] (Cross-reference of related applications)

[0001] This application claims priority to U.S. Provisional Patent Application No. 62 / 953,674, filed on 26 December 2019, entitled “DUAL ELECTROLYTE APPROACH TO INCREASE ENERGY DENSITY OF AQUEOUS METAL-BASED BATTERIES,” which is incorporated herein by reference for all purposes.

[0002] (Description of research and development funded by the federal government)

[0002] None. [Background technology]

[0003]

[0003] Energy storage systems such as batteries are needed for a variety of applications, including grid-based systems, electric vehicles, solar batteries, and uninterruptible power supplies. Currently, lithium-ion batteries and lead-acid batteries dominate the market, but they are expensive, flammable, and contain toxic elements. Water-based metal anode systems, such as zinc (Zn) anode batteries, can compete with lithium and lead in terms of volumetric and gravimetric energy density. They are typically marketed as primary batteries because they can only be used once due to the irreversibility of their active material after complete discharge. [Overview of the Initiative]

[0004]

[0004] In some embodiments, the dual electrolyte battery includes a cathode, an anode, a cathode liquid in contact with the cathode, and an anodic liquid in contact with the anode. The cathode liquid includes a first gelled electrolyte, and the anodic liquid includes a second gelled electrolyte. The concentration of the electrolyte in the anodic liquid is higher than the concentration of the electrolyte in the cathode liquid.

[0005]

[0005] In some embodiments, the dual electrolyte battery includes a cathode, an anode, a cathode liquid in contact with the cathode, and an anodic liquid in contact with the anode. The cathode liquid includes a first gelled electrolyte, and the anodic liquid includes a second gelled electrolyte. The first and second gelled electrolytes contain hydroxide, and the concentration of hydroxide in the anodic liquid is higher than the concentration of hydroxide in the cathode liquid.

[0006]

[0006] In some embodiments, a method for forming a dual electrolyte cell includes placing a cathode liquid in contact with the cathode, placing an anode liquid in contact with the anode, and placing at least one separator or buffer layer between the anode liquid and the cathode liquid. The cathode liquid comprises a first gelled electrolyte, and the anode liquid comprises a second gelled electrolyte. The concentration of hydroxide in the anode liquid is higher than the concentration of hydroxide in the cathode liquid.

[0007]

[0007] These and other features will be more clearly understood from the following detailed description, which is made in conjunction with the accompanying claims. [Brief explanation of the drawing]

[0008]

[0008] For a more complete understanding of the present disclosure and its advantages, similar reference numbers indicate similar parts and refer to the following brief description made in connection with the accompanying drawings and detailed description. [Figure 1]

[0009] This graph shows the ionic conductivity, zinc oxide solubility, and gas generation from Zn powder as a function of KOH concentration. [Figure 2]

[0010] This shows the open-circuit voltage (OCV) of the MnO2 electrode and Zn electrode at different KOH concentrations. [Figure 3A]

[0011] This shows schematic diagrams of dual electrolyte MnO2|Zn batteries according to several embodiments. [Figure 3B]

[0011] This shows a schematic diagram of a double electrolyte MnO2|Zn battery according to several embodiments. [Figure 3C]

[0011] Schematic diagram of a dual electrolyte MnO2|Zn battery according to some embodiments is shown. [Figure 3D]

[0011] Schematic diagram of a dual electrolyte MnO2|Zn battery according to some embodiments is shown. [Figure 4]

[0012] A graph showing the change in KOH concentration after the polymerization process is shown. When neutralized with acrylic acid, the KOH concentration decreases. [Figure 5]

[0013] Gelation times with different KOH concentrations are shown. [Figure 6]

[0014] The potential-time curve of the MnO2 electrode cycle at 40% utilization of its theoretical capacity of 1 electron (308 mAh / g) in 10% KOH aqueous solution is shown. [Figure 7]

[0015] The potential-time curve of the Zn electrode cycle in PGE is shown. [Figure 8]

[0016] The full cell discharge performance of the MnO2 cathode in low-concentration PGE and the Zn anode in high-concentration PGE to obtain 100% of its theoretical capacity of 1 electron (308 mAh / g) is shown. [Figure 9]

[0017] The full cell cycle performance of the MnO2 cathode in low-concentration PGE and the Zn porous anode in high-concentration PGE to obtain 40% of its theoretical capacity of 1 electron (308 mAh / g) is shown. [Figure 10]

[0018] The full cell cycle performance of the MnO2 cathode in low-concentration PGE with graphite mixed in and the Zn mesh anode in high-concentration PGE to obtain 40% of its theoretical capacity of 1 electron (308 mAh / g) is shown. [Figure 11]

[0019] The full cell cycle performance of the MnO2 cathode in low-concentration PGE and the Zn mesh anode in high-concentration PGE to obtain 40% of its theoretical capacity of 1 electron (308 mAh / g) is shown.

DETAILED DESCRIPTION OF THE INVENTION

[0009]

[0020] In the present disclosure, the terms "negative electrode" and "anode" are both used to mean "negative electrode". Similarly, the terms "positive electrode" and "cathode" are both used to mean "positive electrode". A reference to only "electrode" may refer to an anode, a cathode, or both. A reference to the term "primary battery" (e.g., "primary battery", "primary electrochemical cell", or "primary cell") refers to a cell or battery that is disposed of and replaced after one discharge. The term "secondary battery" (e.g., "secondary battery", "secondary electrochemical cell", or "secondary cell") refers to a cell or battery that can be recharged and reused more than once. As used herein, "catholyte" refers to an electrolytic solution that contacts the cathode without directly contacting the anode, and "anolyte" refers to an electrolytic solution that contacts the anode without directly contacting the cathode. The term simply "electrolyte" may refer to an electrolyte that directly contacts the catholyte, the anolyte, or both the anode and the cathode.

[0010]

[0021] Energy storage systems such as batteries are required for various applications such as grid-based, electric vehicles, solar batteries, and uninterruptible power supply devices. Currently, lithium-ion batteries and lead-acid batteries dominate the market, but they are expensive, flammable, and contain toxic elements. Aqueous-based metal anode systems such as zinc (Zn) anode batteries can compete with lithium and lead in terms of volume and weight energy density when combined with a cathode of an inexpensive and abundant material such as manganese dioxide (MnO2). These batteries can supply amounts greater than 400 Wh / L in an aqueous alkaline electrolyte. High energy density is possible because the theoretical capacities of MnO2 and Zn based on the first and second electron reactions are as high as about 617 mAh / g and about 820 mAh / g, respectively.

[0011]

[0022] Attempting to achieve maximum utilization leads to irreversibility, resulting in problems such as volume expansion, collapse of the crystal structure to form spinel, redistribution of active material, zinc poisoning of the cathode, passivation of the metal anode, and dendritic short circuits. Potassium hydroxide (KOH), the electrolyte, is the cause of some of the problems mentioned. During discharge, Mn 4 + The condition is 3 + This reduces the amount of active Mn, leading to increased solubility at high KOH concentrations when used in large volumes. 3+ Ion loss causes a loss of battery capacity. Also, dissolved Mn 3+ The ions also dissociate into Mn 4+ and Mn 2+ It can form ions, which can lead to the formation of lower oxides such as spinel (Mn3O4) and pyrochlorite (Mn(OH)2). Zn can form dissolved zincate ions (Zn(OH)4) 2- The reaction becomes even more complex as it achieves its capacity through a dissolution reaction that forms [anode]. The dissolved zincate ions also react with dissolved Mn ions to form inert Zn spinel such as ZnMn2O4. The Zn anode can also form resinous crystals during charging that could penetrate the separator and short-circuit the battery.

[0012]

[0023] Another problem with Zn anodes is the active redistribution of the active material during the dissolution reaction, which leads to the loss of active ions from the current collector and, consequently, a loss of capacity. The cathode also undergoes a large volume expansion during its discharge reaction as protons from the electrolyte are inserted into its crystal structure, which leads to the detachment of the active material from the current collector and, again, a loss of capacity.

[0013]

[0024] This disclosure discloses a method and procedure for preparing polymer gel electrolytes (PGEs) using KOH in a framework adapted in terms of concentration, viscosity, ionic conductivity, etc., for each electrode. The preparation of the PGEs allows for the use of two electrolyte concentrations in a single cell, and is tuned to obtain improved or optimal performance from the cathode and anode, respectively.

[0014]

[0025] More specifically, in the cells and methods disclosed herein, polymer gel electrolytes (PGEs) can be used at different concentrations for the cathode and anode sides, respectively, and adapted to their properties to achieve improved utilization from each electrode. Since capacity utilization depends on the dissolution of Zn, the Zn anode is gelled preferably with a high KOH concentration to increase the solubility of Zn ions, while the MnO2 cathode is preferably Mn 3+ The PGE is gelled at a low KOH concentration to limit ion solubility. Other additives such as carbon, Teflon, and cellulose fibers may also be added to the PGE to increase electrode capacity utilization and limit gas contamination in the gel. Furthermore, the viscosity of the PGE at the anode may be lower than that at the cathode. This is because, while a higher cathode viscosity may limit the movement of manganese ions from the cathode and zincate ions to the cathode, it may allow gases generated at the anode to move away from the anode.

[0015]

[0026] In some embodiments, a cell is disclosed having a first PGE of concentration A applied to the cathode and a second PGE of concentration B applied to the anode. A separator or buffer layer may be present between the PGEs to prevent mixing. The PGE of concentration A may be lower on the cathode side and the PGE of concentration B may be higher on the anode side. In some embodiments, the PGE of concentration A may have a higher viscosity than the PGE of concentration B on the anode side.

[0016]

[0027] The reasons for designing this dual electrolyte type cell are explained with reference to Figure 1. Generally, zinc anodes achieve their capacity through a dissolution mechanism, so the solubility of zinc ions is important in the electrolyte. However, Zn anodes also corrode in hydroxide electrolytes such as KOH, releasing hydrogen. In cell operation, the release of this gas is important because it is either released into the atmosphere or reacts with catalysts in the cell to form water again. Subsequently, the viscosity of the PGE on the anode side can be adjusted to allow for the dissolution of Zn and the release of hydrogen gas. Also, a higher concentration of hydroxide in the electrolyte can be used to allow for the dissolution of more zinc in the PGE on the anode side, thereby improving the utilization of its capacity. On the cathode side, the concentration of hydroxide in the electrolyte is lower to limit the solubility of Mn in the PGE while allowing for high utilization of the one-electron capacity, and the viscosity of the PGE on the cathode side should be high enough to limit the diffusion of zincate ions from the anode side to the cathode side.

[0017]

[0028] Another advantage of having a dual electrolyte cell with a lower alkali concentration of PGE on the cathode side and a higher alkali concentration of PGE on the anode side is the increase in cell potential, as shown in Figure 2. As shown, the lower alkali concentration on the cathode side and the higher alkali concentration on the anode side can increase the cell potential, which can result in a higher mean discharge voltage and, consequently, higher energy from the cell.

[0018]

[0029] Referring to Figures 3A to 3D, the battery 10 may have a housing 7, a cathode 12 which may include a cathode current collector 1 and a cathode material 2, and an anode 13. In some embodiments, the anode 13 may include an anode current collector 4 and an anode material 5. Note that the scale of the components in Figures 3A to 3D may not be accurate as features are represented to clearly show the electrolyte around the anode 13 and cathode 12. Figures 3A to 3C show a prismatic battery configuration having a single anode 13 and cathode 12. In another embodiment, the battery may be a cylindrical battery (as shown in Figure 3D, for example) having concentrically arranged electrodes, or a rolled configuration in which the anode and cathode are layered and then rolled to form a jelly roll configuration. The cathode current collector 1 and cathode material 2 are collectively referred to as the cathode 12 or positive electrode 12, as shown in Figure 2. Similarly, the anode material 5 having an optional anode current collector 4 may be collectively referred to as the anode 13 or negative electrode 13. The electrolyte may come into contact with the cathode 12 and the anode 13. As described in more detail herein, the electrolyte 15 in contact with both the cathode 12 and the anode may be the same with different concentrations, or different electrolyte compositions may be used with the anode 13 and the cathode 12 to modify the properties of the battery 10 in some embodiments.

[0019]

[0030] In some embodiments, the battery 10 may comprise one or more cathodes 12 and one or more anodes 13, which may exist in any configuration or shape factor. When multiple anodes 13 and / or multiple cathodes 12 are present, the electrodes may be configured in a layered configuration such that the electrodes alternate (e.g., anode, cathode, anode). Any number of anodes 13 and / or cathodes 12 may be present to provide a desired capacity and / or output voltage. In a jelly roll configuration (e.g., as shown in Figure 3D), multiple cathodes 12 and anodes 13 may be used in a layered configuration or rolled to form a rolled configuration with alternating layers, but the battery 10 may have only one cathode 12 and one anode 13 in a rolled configuration such that the cross-section of the battery 10 includes a layered configuration of alternating electrodes.

[0020]

[0031] In one embodiment, the housing 7 includes a molded box or container containing an electrolyte, which is generally inactive to the electrolyte solution in the battery 10. In one embodiment, the housing 7 includes a polymer (e.g., a polypropylene molded box, an acrylic polymer molded box, etc.), a metal coating, etc.

[0021]

[0032] The cathode 12 may comprise a mixture of components including an electrochemical active material. Additional components, such as binders, conductive materials, and / or one or more additional components, may be optionally included, which may help improve the lifespan, rechargeability, and electrochemical properties of the cathode 12. The cathode 12 may comprise the cathode material 2 (e.g., electroactive material, additives, etc.). The cathode may contain active material in an amount between about 1% by weight and about 95% by weight. Suitable cathode material 2 includes manganese dioxide, copper manganese oxide, hausmannite, manganese oxide, copper intercalated bismuth barnesite, barnesite, todolokite, ramsdelite, pyrolsite, pyrochroite, silver oxide, silver dioxide, silver, nickel oxyhydroxide, nickel hydroxide, nickel, lead oxide, copper oxide, copper dioxide, lead, lead dioxide (α and β), potassium persulfate, sodium persulfate, ammonium persulfate, potassium permanganate, calcium permanganate, barium permanganate, silver permanganate, ammonium permanganate, peroxide, gold, perchlorate, cobalt oxide (CoO, CoO2, Co3O4), lithium cobalt oxide, sodium cobalt oxide, perchlor The cathode may include, but is not limited to, salts, nickel oxides, bromine, mercury, vanadium oxides, bismuth vanadium oxides, hydroquinones, calix[4]quinones, tetrachlorobenzoquinones, 1,4-naphthoquinones, 9,10-anthraquinones, 1,2-naphthaquinones, 9,10-phenanthrenequinones, nitroxide-oxoammonium cation redox pairs such as 2,2,6,6-tetramethylpiperidine-1-yl)oxyl(TEMPO), carbon, 2,3-dicyano-5,6-dichlorodicyanoquinones, tetracyanoethylenes, sulfur trioxides, ozone, oxygen, air, lithium nickel manganese cobalt oxides, sulfur, lithium iron phosphate, lithium copper oxides, lithium copper oxyphosphate, or any combination thereof. In some embodiments, the cathode may include an air electrode.

[0022]

[0033] In some embodiments, the cathode material 2 can be based on one or more polymorphic MnO2 including electrolytic manganese dioxide (EMD), α-MnO2, β-MnO2, γ-MnO2, δ-MnO2, ε-MnO2, or λ-MnO2. Other forms of MnO2 such as hydrated MnO2, pyrolusite, birnessite, ramsdellite, hollandite, romanechite, todorokite, lithiophorite, calcoffinite, sodium- or potassium-rich birnessite, cryptomelane, buserite, manganese oxyhydroxide (MnOOH), α-MnOOH, γ-MnOOH, β-MnOOH, manganese hydroxide [Mn(OH)2], partially or fully protonated manganese dioxide, Mn3O4, Mn2O3, bixbyite, MnO, lithium manganese dioxide (LiMn2O4, Li2MnO3), CuMn2O4, aluminum manganese oxide, zinc manganese dioxide, bismuth manganese oxide, birnessite intercalated with copper, bismuth birnessite intercalated with copper, tin-doped manganese oxide, magnesium manganese oxide, or any combination thereof may also be present. Generally, in the cyclic form of the cathode manganese dioxide, in some embodiments, it can have a layered structure containing δ-MnO2, which is said to be almost the same as birnessite. When non-birnessite polymorphic forms of manganese dioxide are used, they can be converted in situ to birnessite by one or more state adjustment cycles, as described in more detail below. For example, a complete or partial discharge (e.g., between about 20% and about 100% of the second electron capacity of the cathode) is performed until the end of the second electron stage of MnO2, followed by recharging to that Mn 4+ state to become manganese dioxide in the birnessite phase.

[0023]

[0034] By adding conductive additives such as conductive carbon, it is possible to increase the load of the electroactive material in the cathode material, thereby increasing the volumetric and gravimetric energy density. In some embodiments, the conductive additive may include graphite, carbon fiber, carbon black, acetylene black, single-walled carbon nanotubes, multi-walled carbon nanotubes, nickel or copper-coated carbon nanotubes, dispersions of single-walled carbon nanotubes, dispersions of multi-walled carbon nanotubes, graphene, graphene oxide, or combinations thereof. A higher load of the electroactive material in the cathode is desirable in some embodiments to increase the energy density. Other examples of conductive carbon include TIMREX primary synthetic graphite (all types), TIMREX natural flake graphite (all types), TIMREX MB, MK, MX, KC, B, LB grades (e.g., KS15, KS44, KC44, MB15, MB25, MK15, MK25, MK44, MX15, MX25, BNB90, LB family), TIMREX dispersions; ENASCO 150G, 210G, 250G, 260G, 350G, 150P, 250P; SUPER P, SUPER P Li, carbon black (e.g., Ketjenblack EC-300J, Ketjenblack EC-600JD, Ketjenblack EC-600JD powder), acetylene black, carbon nanotubes (single-walled or multi-walled), Zenyatta graphite, and / or combinations thereof.

[0024]

[0035] In some embodiments, the particle size range of the conductive additive may be between about 1 and about 50 microns, or between about 2 and about 30 microns, or between about 5 and about 15 microns. The total mass percentage of the conductive additive in cathode material 2 may be between about 5% and about 99%, or between about 10% and about 80%. In some embodiments, the electroactive component of cathode material 2 may be between 1% and 99% by weight of cathode material 2, and the conductive additive may be between 1% and 99% by weight.

[0025]

[0036] The cathode material 2 may also contain conductive components. The addition of conductive components, such as metal additives, to the cathode material 2 may be achieved by adding one or more metal powders, such as nickel powder, to the cathode material 2. The conductive metal component may be present in the cathode material 2 at a concentration between about 0 and 30% by weight. The conductive metal component may be, for example, nickel, copper, silver, gold, tin, cobalt, antimony, brass, bronze, aluminum, calcium, iron, or platinum. In one embodiment, the conductive metal component is a powder. In some embodiments, the conductive component may be added as an oxide and / or salt. For example, the conductive component may be cobalt oxide, cobalt hydroxide, lead oxide, lead hydroxide, or a combination thereof. In some embodiments, a second conductive metal component is added to function as a supporting conductive framework for the first and second electronic reactions to occur. The second electronic reaction involves Mn 3+ The ions dissolve in the electrolyte and precipitate on materials such as graphite, undergoing a dissolution-precipitation reaction, leading to an electrochemical reaction and the formation of non-conductive manganese hydroxide [Mn(OH)2]. This ultimately results in a capacity fade in subsequent cycles. Suitable conductive components that can help reduce the solubility of manganese ions include transition metals such as Ni, Co, Fe, and Ti, and metals such as Ag, Au, Al, and Ca. Oxides and salts of such metals are also suitable. Transition metals like Co, as well as Mn 3+ This can help reduce the solubility of ions. Such conductive metal components may be incorporated into the electrode by chemical or physical means (e.g., ball mill, mortar and pestle, spex mixture). An example of such an electrode contains 5-95% barnesite, 5-95% conductive carbon, 0-50% conductive component (e.g., conductive metal), and 1-10% binder.

[0026]

[0037] In some embodiments, the binder may be used together with the cathode material 2. The binder may be present in a concentration between about 0–10% by weight of the cathode material, or between about 1–5% by weight. In some embodiments, the binder may be used as a thickener and strong binder and comprises a water-soluble cellulose hydrogel crosslinked with a conductive polymer with good mechanical strength. The binder may also be a cellulose film sold as cellophane. The binder may be created by physically crosslinking a water-soluble cellulose hydrogel with a polymer by repeating cooling and thawing cycles. In some embodiments, the binder may comprise a 0–10% by weight carboxymethylcellulose (CMC) solution crosslinked with 0–10% by weight polyvinyl alcohol (PVA) based on equal volume. The binder exhibits superior performance compared to conventionally used PTFE (polytetrafluoroethylene). Although PTFE is a high-resistance material, it is widely used in the industry due to its excellent rollability. This, however, does not preclude the use of PTFE as a binder. A mixture of PTFE, an aqueous binder, and some conductive carbon can be used to create a rollable binder. The use of an aqueous binder can help achieve a significant portion of the two-electron capacity by minimizing capacity loss over many cycles. In some embodiments, the binder may be aqueous, having excellent water retention and adhesive properties, and helping to maintain conductivity compared to the same cathode using a PTFE binder instead. Suitable aqueous hydrogels include, but are not limited to, methylcellulose (MC), carboxymethylcellulose (CMC), hydroxypropylcellulose (HPH), hydroxypropylmethylcellulose (HPMC), hydroxyethylmethylcellulose (HEMC), carboxymethylhydroxyethylcellulose, hydroxyethylcellulose (HEC), and combinations thereof. Crosslinked polymers include polyvinyl alcohol, polyvinyl acetate, polyaniline, polyvinylpyrrolidone, polyvinylidene fluoride, polypyrrole, and combinations thereof.In some embodiments, a 0-10 wt% solution of cellulose hydrogen in water can be crosslinked with a 0-10 wt% solution of a crosslinked polymer by, for example, repeated freeze / thaw cycles, radiation treatment, and / or chemicals (e.g., epichlorohydrin). The aqueous binder may be mixed with 0-5% PTFE to improve manufacturability.

[0027]

[0038] Cathode material 2 may also contain additional elements. These additional elements may be present in the cathode material, including bismuth compounds and / or copper / copper compounds, which together enable improved constant-current battery cycling of the cathode. When present as barnesite, copper and / or bismuth may be incorporated into the layered nanostructure of the barnesite. The resulting barnesite cathode material may exhibit improved cycling and long-term performance due to the copper and bismuth incorporated into the crystalline and nanostructure of the barnesite.

[0028]

[0039] Bismuth compounds can be incorporated into cathode 12 as inorganic or organic salts of bismuth (oxidation states 5, 4, 3, 2, or 1), as bismuth oxides, or as bismuth metal (i.e., elemental bismuth). Bismuth compounds may be present in the cathode material 2 at a concentration between approximately 1 and 20% by weight of the cathode material 2. Examples of bismuth compounds include bismuth chloride, bismuth bromide, bismuth fluoride, bismuth iodide, bismuth sulfate, bismuth nitrate, bismuth trichloride, bismuth citrate, bismuth telluride, bismuth selenide, bismuth subsalicylate, bismuth neodecanoate, bismuth carbonate, bismuth subgallate, bismuth strontium calcium copper oxide, bismuth acetate, bismuth trifluoromethanesulfonate, bismuth nitrate oxide, bismuth gallate hydrate, bismuth phosphate, and bismuth cobalt zinc oxide. Examples include bismuth sulfite agar, bismuth oxychloride, bismuth aluminate hydrate, bismus mustangsten oxide, bismuth lead strontium calcium copper oxide, bismuth antimonide, bismuth antimony telluride, yttria-stabilized bismuth oxide, bismuth-lead alloy, bismuth ammonium citrate, 2-naptol bismuth salt, dichloro(tri-o-tolyl)bismuth, dichlorodiphenyl(p-tolyl)bismuth, triphenylbismuth, and / or combinations thereof.

[0029]

[0040] Copper compounds can be incorporated into cathode 12 as organic or inorganic salts of copper (oxidation states 1, 2, 3, or 4), as copper oxides, or as metal copper (i.e., elemental copper). Copper compounds may be present in concentrations between about 1 and 70% by weight of cathode material 2. In some embodiments, copper compounds are present in concentrations between about 5 and 50% by weight of cathode material 2. In other embodiments, copper compounds are present in concentrations between about 10 and 50% by weight of cathode material 2. In yet another embodiment, copper compounds are present in concentrations between about 5 and 20% by weight of cathode material 2. Examples of copper compounds include copper and copper salts such as copper-aluminum oxide, copper oxide (I), copper oxide (II), and / or copper salts in oxidation states +1, +2, +3, or +4, including but not limited to copper nitrate, copper sulfate, and copper chloride. The effect of copper is to alter the oxidation and reduction voltage of bismuth. This results in a cathode that is completely reversible during constant current cycling, compared to bismuth-modified MnO2 which cannot withstand constant current cycling.

[0030]

[0041] The cathode 12 can be manufactured using a method that is feasible in large-scale manufacturing. In the case of a MnO2 cathode, the cathode 12 may be capable of delivering the entire second electron capacity of the MnO2. In some embodiments, the cathode material 2 comprises 2 to 30 wt% conductive carbon, 0 to 30% conductive metal additive, 1 to 70 wt% copper compound, 1 to 20 wt% bismuth compound, 0 to 10 wt% binder, and barnesite or EMD. In another embodiment, the cathode material comprises 2 to 30 wt% conductive carbon, 0 to 30% conductive metal additive, 1 to 20 wt% bismuth compound, 0 to 10 wt% binder, and barnesite or EMD. In one embodiment, the cathode material mainly consists of 2-30% by weight of conductive carbon, 0-30% of conductive metal additives, 1-70% by weight of copper compound, 1-20% by weight of bismuth compound, and 0-10% by weight of binder, with the remainder being barnesite or EMD. In another embodiment, the cathode material mainly consists of 2-30% by weight of conductive carbon, 0-30% of conductive metal additives, 1-20% by weight of bismuth compound, and 0-10% by weight of binder, with the remainder being barnesite or EMD.

[0031]

[0042] The resulting cathode may have a porosity ranging from 20% to 85% when measured by mercury intrusion porosimetry. Porosity can be measured using the version of ASTM D4284-12, “Standard Test Method for Determining Pore Volume Distribution of Catalysts and Catalyst Carriers by Mercury Intrusion Porosimetry,” as of the filing date of this application.

[0032]

[0043] The cathode material 2 may be formed on a cathode current collector 1 formed from a conductive material, which serves as an electrical connection between the cathode material and one or more external electrical connections. In some embodiments, the cathode current collector 1 may be, for example, carbon, lead, nickel, steel (e.g., stainless steel), nickel-plated steel, nickel-plated copper, tin-plated steel, copper-plated nickel, silver-plated copper, copper, magnesium, aluminum, tin, iron, platinum, silver, gold, titanium, bismuth, titanium, half nickel and half copper, or any combination thereof. In some embodiments, the current collector 1 may include carbon felt or a conductive polymer mesh. The cathode current collector may be formed from mesh (e.g., expanded mesh, woven mesh, etc.), perforated metal, foam, foil, felt, fibrous structure, porous block structure, perforated foil, wire screen, packaging assembly, or any combination thereof. In some embodiments, the current collector may be formed in a pocket assembly in which pockets are capable of holding the cathode material 2 within the current collector 1, or may form part of a pocket assembly. A tab (for example, a portion of the cathode current collector 1 extending outside the cathode material 2, as shown at the top of cathode 12 in Figure 3B) may be coupled to the current collector to provide an electrical connection between the external power source and the current collector.

[0033]

[0044] The cathode material 2 can be pressed onto the cathode current collector 1 to form a cathode 12. For example, the cathode material 2 can be used at a pressure between 1,000 psi and 20,000 psi (6.9 × 10⁻¹⁰). 6 Pascal's 1.4 × 10 8 The cathode material 2 can be bonded to the cathode current collector 1 by pressing it with a pressure of (Pascals). The cathode material 2 may be bonded to the cathode current collector 1 as a paste. The resulting thickness of the cathode 12 may be between approximately 0.1 mm and approximately 5 mm.

[0034]

[0045] The use of electrolytes having different properties as described herein may enable the use of a variety of anode materials. In some embodiments, the anode may include lithium, zinc, aluminum, magnesium, iron, calcium, strontium, lanthanum, potassium, sodium, zirconium, titanium, titanium oxide, indium, indium oxide, indium hydroxide, zinc oxide, Mn3O4, heterolite (ZnMn2O4), vanadium, tin, tin oxide, barium hydroxide, barium, cesium, aluminum hydroxide, copper, bismuth, silicon, carbon, and any mixture of these materials. The cells described herein may be formed by pairing any of the cathode materials described herein with any of the anode materials described above to generate a voltage in the presence of a suitable electrolyte (e.g., suitable anode and cathode liquids).

[0035]

[0046] In some embodiments, the anode material 5 may contain zinc, which may exist as elemental zinc and / or zinc oxide. In some embodiments, the Zn anode mixture comprises Zn, zinc oxide (ZnO), an electronically conductive material, and a binder. Zn may be present in the anode material 5 in amounts of about 50% to about 90% by weight, or about 60% to about 80% by weight, or about 65% to about 75% by weight, based on the total weight of the anode material. Additional elements that may be present in the anode in addition to or instead of zinc include, but are not limited to, lithium, aluminum, magnesium, iron, cadmium, and combinations thereof, and each element may be present in the same or equivalent amounts as zinc as described herein.

[0036]

[0047] In some embodiments, the anode material 5 may contain zinc oxide (ZnO) in amounts of about 5% to about 20% by weight, or about 5% to about 15% by weight, or about 5% to about 10% by weight, based on the total weight of the anode material. As can be appreciated by those skilled in the art, utilizing this disclosure, the purpose of the ZnO in the anode mixture is to provide a source of Zn during the recharging step, and the zinc present may be converted between zinc and zinc oxide during the charging and discharging steps.

[0037]

[0048] In one embodiment, the electrically conductive material may be optionally present in the anode material in an amount of about 5% to about 20% by weight, or about 5% to about 15% by weight, or about 5% to about 10% by weight, based on the total weight of the anode material. As will be appreciated by those skilled in the art, utilizing this disclosure, the electrically conductive material may be used in the anode mixture as a conductive agent, for example, to enhance the overall electrical conductivity of the anode mixture. Non-limiting examples of electrically conductive materials suitable for use include any of the conductive carbons described herein, such as carbon, graphite, graphite powder, graphite powder flakes, graphite powder spheroids, carbon black, activated carbon, conductive carbon, amorphous carbon, glassy carbon, or combinations thereof. The conductive material may also include, but is not limited to, any conductive carbon material described with respect to the cathode material, including acetylene black, single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, or any combination thereof.

[0038]

[0049] Anode material 5 may also contain a binder. Generally, the binder functions in contact with the current collector to hold the electroactive material particles together. The binder may be present in a concentration of 0 to 10% by weight. The binder may include water-soluble cellulose-based hydrogels used as thickeners and strong binders, such as methylcellulose (MC), carboxymethylcellulose (CMC), hydroxypropylcellulose (HPH), hydroxypropylmethylcellulose (HPMC), hydroxyethylmethylcellulose (HEMC), carboxymethylhydroxyethylcellulose, and hydroxyethylcellulose (HEC), which are crosslinked with conductive polymers such as polyvinyl alcohol, polyvinyl acetate, polyaniline, polyvinylpyrrolidone, polyvinylidene fluoride, and polypyrrole with good mechanical strength. The binder may also be a cellulose film sold as cellophane. The binder may also be PTFE, a high-resistance material, which is widely used in the industry due to its excellent rollability. In some embodiments, the binder may be present in the anode material in an amount of about 2% to about 10% by weight, or about 2% to about 7% by weight, or about 4% to about 6% by weight, based on the total weight of the anode material.

[0039]

[0050] In some embodiments, tabs or other electrical connections may still be provided to the anode material 5, but the anode material 5 may be used by itself without a separate anode current collector 4. In this embodiment, the anode material may have the form or structure of foil, mesh, perforated layer, foam, felt, or powder. For example, the anode may include a metal foil electrode, a mesh electrode, or a perforated metal foil electrode.

[0040]

[0051] In some embodiments, the anode 13 may include an optional anode current collector 4. The anode current collector 4 may be used with the anode 13, including any of those described with respect to the cathode 12. The anode material 5 may be pressed against the anode current collector 4 to form the anode 13. For example, the anode material 5 may have a pressure between 1,000 psi and 20,000 psi (6.9 × 10⁻¹⁰). 6Pascal's 1.4 × 10 8 The anode material 5 can be bonded to the anode current collector 4 by pressing with a pressure of (Pascals). The anode material 5 may be bonded to the anode current collector 4 as a paste. The tabs of the anode current collector 4, if present, may extend outwards from the device to form a current collector tab. The resulting thickness of the anode 13 may be between approximately 0.1 mm and approximately 5 mm.

[0041]

[0052] As shown in Figure 3B, the battery 10 does not need to have a separator. The ability to form the battery 10 without a separator may allow for a reduction in the overall cost of the battery while having the same or comparable performance as a battery with a separator. The use of PGE can perform the function of a separator by forming a physical barrier between the anode 13 and the cathode 12 to prevent short circuits.

[0042]

[0053] In some embodiments, such as those shown in Figures 3A and 3C, the separator 9 (e.g., as shown in Figure 3C) and / or buffer layer 21 (e.g., as shown in Figure 3A) may be placed between the anode 13 and the cathode 12 when the electrodes are configured in a battery. Although shown placed between the anode 13 and the cathode 12, the separator 9 may be used to enclose one or more of the anode 13 and / or cathode 12, or one or more anodes 13 and / or cathode 12 when multiple anodes 13 and cathode 12 are present.

[0043]

[0054] The separator 9 may comprise one or more layers. For example, when a separator is used, 1 to 5 layers of separator may be applied between adjacent electrodes. The separator may be formed from suitable materials such as nylon, polyester, polyethylene, polypropylene, poly(tetrafluoroethylene) (PTFE), poly(vinyl chloride) (PVC), polyvinyl alcohol, cellulose, or any combination thereof. Suitable layer and separator forms may include, but are not limited to, sintered polymer film membranes, polyolefin membranes, polyolefin nonwoven membranes, cellulose membranes, cellophane, battery-grade cellophane, hydrophilic modified polyolefin membranes, or polymer separator layers, or combinations thereof. As used herein, the phrase "hydrophilic modified" refers to a material with a contact angle with water of less than 45°. In another embodiment, the contact angle with water is less than 30°. In yet another embodiment, the contact angle with water is less than 20°. The polyolefin may be modified, for example, by the addition of TRITON X-100™ or by oxygen plasma treatment. In some embodiments, separator 9 may include a microporous separator of the CELGARD® brand. In one embodiment, separator 9 may include the FS 2192 SG film, a polyolefin nonwoven film commercially available from Freudenberg, Germany. In some embodiments, the separator may include lithium superionic conductors (LISICON®), sodium superionic conductors (NASICON), NAFION®, bipolar films, water electrolytic films, composites of polyvinyl alcohol and graphene oxide, polyvinyl alcohol, crosslinked polyvinyl alcohol, or combinations thereof.

[0044]

[0055] The separator 9 may contain a variety of materials, but when one or more separators are present, using PGE as the electrolyte may allow for the use of a relatively inexpensive separator 9. For example, the separator 9 may include CELLOPHANE®, polyvinyl alcohol, CELGARD®, a composite of polyvinyl alcohol and graphene oxide, cross-linked polyvinyl alcohol, PELLON®, and / or a carbon-polyvinyl alcohol composite. The use of separator 9 may help improve the cycle life of the battery 20, but is not essential in all embodiments.

[0045]

[0056] When the buffer layer 21 is used, it may be used alone or in combination with the separator 9. The buffer layer 21 may contain a gelled solution that has the same electrolyte composition as the anode and / or cathode. For example, the buffer layer 21 may be PGE as described herein. One or more additives, such as calcium hydroxide, layered double hydroxides such as hydrotalcites, quintinite, vogelite, magnesium hydroxide, or a combination thereof, may also be present in the buffer layer 21. For example, if the anode and cathode have the same composition and only differ in composition and / or viscosity, the electrolyte concentration of the buffer layer may be the same as that of the anode or cathode, or may be between the concentrations of the anode and cathode. The buffer layer may have a higher viscosity than either the anode or cathode to help prevent mixing between the anode and cathode, as well as to restrict ion movement between them.

[0046]

[0057] As shown in Figures 3A to 3D, the cathode liquid 3 may be in contact with the cathode 12, and the anode liquid 6 may be in contact with the anode 13. As described in more detail herein, one or both of the cathode liquid 3 and / or the anode liquid 6 may be polymerized or gelled to form a separate gel electrolyte to prevent mixing between the two electrolyte solutions. The cathode liquid 3 may be placed in the housing 10 in contact with the cathode material 2. In some embodiments, the anode liquid 6 may be polymerized or gelled, and the cathode liquid 3 may be liquid. Polymerization of the anode liquid 6 may prevent mixing between the cathode liquid 3 and the anode liquid 6, even if the cathode liquid 3 is liquid. In some embodiments, both the cathode liquid 3 and the anode liquid 6 are gelled.

[0047]

[0058] The cathode solution 3 can be an acidic or neutral solution, and its pH can be between -1.2 and 7. The cathode solution 3 can be used under temperature conditions ranging from 0°C to 200°C. In some embodiments, the cathode solution may contain an acid such as a mineral acid (e.g., hydrochloric acid, nitric acid, sulfuric acid, etc.). In the case of an acidic cathode solution composition, the acid concentration can be between approximately 0 M and approximately 16 M. In some embodiments, the cathode solution may contain potassium permanganate, sodium permanganate, lithium permanganate, calcium permanganate, manganese sulfate, manganese chloride, manganese nitrate, manganese perchlorate, manganese acetate, bis(trifluoromethanesulfonic acid)manganese, manganese triflate, manganese carbonate, manganese oxalate, manganese fluorosilicate, manganese ferrocyanide, manganese bromide, magnesium sulfate, ammonium chloride, ammonium sulfate, ammonium hydroxide, zinc sulfate, zinc triflate, zinc acetate, zinc nitrate, bismuth chloride, bismuth nitrate, nitric acid, sulfuric acid, hydrochloric acid, sodium sulfate, sulfuric acid The solution may contain potassium, cobalt sulfate, lead sulfate, sodium hydroxide, potassium hydroxide, titanium sulfate, titanium chloride, lithium nitrate, lithium chloride, lithium bromide, lithium bicarbonate, lithium acetate, lithium sulfate, lithium nitrate, lithium nitrite, lithium hydroxide, lithium perchlorate, lithium oxalate, lithium fluoride, lithium carbonate, lithium sulfate, lithium bromate, polyvinyl alcohol, carboxymethylcellulose, xanthan gum, carrageenan, acrylamide, potassium persulfate, sodium persulfate, ammonium persulfate, N,N'-methylenebisacrylamide, or any combination thereof. For example, the cathode solution may contain manganese sulfate mixed with sulfuric acid, or potassium permanganate mixed with sulfuric acid. Other dopants for this solution may be zinc sulfate, lead sulfate, titanium disulfide, titanium sulfate hydrate, silver sulfate, cobalt sulfate, and nickel sulfate. In some embodiments, the cathode solution may contain manganese sulfate, ammonium chloride, ammonium sulfate, manganese acetate, potassium permanganate, and / or permanganate salts, and the concentration of the additive may be between 0 and 10 M. Depending on the type of manganese salt used, the voltage of the battery system may vary.For example, with manganese sulfate electrolyte, the voltage of SS-HiVAB is approximately 2.45 to 2.5V, while with potassium permanganate electrolyte, the voltage of SS-HiVAB is approximately 2.8 to 2.9V.

[0048]

[0059] In some embodiments, the cathode solution may contain permanganate. Permanganate has a high positive potential. This may allow for an increase in the overall cell potential within the battery 10. When present, the permanganate may be present in a molar ratio of permanganate to acid (e.g., mineral acid such as hydrochloric acid or sulfuric acid) between approximately 5:1 and approximately 1:5, or approximately 1:1 and approximately 1:6, or approximately 1:2 and approximately 1:4, or approximately 1:3, although the exact amount may vary depending on the expected operating conditions of the battery 10. The concentration of permanganate (e.g., potassium permanganate or a salt of permanganate) may be greater than 0 and less than or equal to 5 M. In some embodiments, the cathode solution contains sulfuric acid, hydrochloric acid, or nitric acid at a concentration greater than 0 and less than or equal to 16 M. The use of permanganates can be advantageous in creating high-voltage batteries, as the resulting battery voltage is approximately 4V when the cathode and anode are MnO2|Zn and approximately 2.8V when the cathode and anode are MnO2|Al. When the cathode and anode contain permanganates, suitable permanganates may include, but are not limited to, potassium permanganate, sodium permanganate, lithium permanganate, calcium permanganate, and combinations thereof.

[0049]

[0060] In some embodiments, the anode may be an alkaline electrolyte, while the cathode may be an acidic or neutral solution. The alkaline electrolyte in the anode may be a hydroxide such as potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, cesium hydroxide, or any combination thereof. The pH of the resulting anode may exceed 7. In some embodiments, the pH of the anode may be between 10 and about 15.13. As described herein, the anode may be polymerized or gelled. The resulting anode may be in a semi-solid state that resists flow within the battery. This may help limit or prevent mixing of the anode and cathode. The anode may be polymerized using any suitable technique, including any of those described herein. Typically, higher concentrations of the alkaline electrolyte are used to increase the solubility of the metal in the gelled state. For example, higher concentrations may be between 25 and 70% by weight of the anode.

[0050]

[0061] In addition to hydroxides, the anode 6 may contain additional components. In some embodiments, the alkaline electrolyte may have zinc oxide, potassium carbonate, potassium iodide, and potassium fluoride as additives. When zinc compounds are present in the anode, the anode may contain zinc sulfate, zinc chloride, zinc acetate, zinc carbonate, zinc chlorate, zinc fluoride, zinc formate, zinc nitrate, zinc oxalate, zinc sulfite, zinc tartrate, zinc cyanide, zinc oxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium chloride, sodium chloride, potassium fluoride, lithium nitrate, lithium chloride, lithium bromide, lithium bicarbonate, lithium acetate, lithium sulfate, lithium permanganate, lithium nitrate, lithium nitrite, lithium nitrite, lithium perchlorate, lithium oxalate, lithium fluoride, lithium carbonate, lithium bromate, acrylic acid, N,N'-methylenebisacrylamide, potassium persulfate, ammonium persulfate, sodium persulfate, or combinations thereof.

[0051]

[0062] In some embodiments, an organic solvent containing a suitable salt may be used as the electrolyte. Suitable organic solvents include, but are not limited to, cyclic carbonates, linear carbonates, dialkyl carbonates, aliphatic carboxylic acid esters, γ-lactones, linear ethers, cyclic ethers, aprotic organic solvents, fluorinated carboxylic acid esters, and combinations thereof. Any suitable additive containing the salts described herein may be used with an organic solvent to form an organic electrolyte for the anode and / or cathode.

[0052]

[0063] In some embodiments, ionic liquids may be used to form gel electrolytes (e.g., gelled anode liquid, gelled cathode liquid, etc.). Ionic liquids may include 1-ethyl-3-methylimidazolium chloride (EMImCl), 1-allyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium chloride, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium tetrachloroaluminate, lithium hexafluorophosphate (LiPF6), lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(oxalato)borate, and combinations thereof. Other ionic liquids are known and may also be used. In some embodiments, EMImCl may be used as an ionic liquid and may be purified before being mixed with aluminum salts to form aluminum ion-conducting electrolytes. Aluminum salts can include aluminum chloride, aluminum acetate, aluminum nitrate, and aluminum bromide. A mixture of EMImCl and aluminum chloride can be prepared by slowly adding a precise amount of aluminum chloride in an inert atmosphere. The mixing ratio of aluminum chloride to EMImCl may be between 5:1 and 1:1, or approximately 1.5:1.

[0053]

[0064] In some embodiments, the water-in-salt electrolyte can be gelled and used as the cathodeliand and / or anodeliand. The water-in-salt electrolyte may contain an electrolyte with a salt concentration above its saturation point. By increasing the salt concentration above the saturation point to form the water-in-salt electrolyte, the activity of water in the aqueous electrolyte can be further reduced. The ionic conductivity of such an electrolyte may be higher than that of a normal aqueous electrolyte. The water-in-salt electrolyte may contain water with a suitable salt above its saturation point, which may include any of the salts and additives described herein for the aqueous anodeliand and / or cathodeliand.

[0054]

[0065] In some embodiments, the compounds in the electrolytes of the anode and cathode may be the same, but their concentrations may differ. In those embodiments, the cathode and anode may contain any of the above compounds for the anode and / or cathode. For example, the anode and cathode may contain hydroxides such as potassium hydroxide. The concentration of hydroxide in contact with the anode may be higher than the concentration of hydroxide in the cathode. When gelled, the viscosities of the anode and cathode may differ. In some embodiments, the viscosity of the cathode may be higher than that of the anode (e.g., resulting in a thicker gel).

[0055]

[0066] The anode liquid and / or cathode liquid may gel within the battery. The polymerization process may be carried out with any electrolyte, including any of those described herein (e.g., organic, aqueous, ionic liquid, water in saline, etc.). Several polymerization techniques may be used to form the gel / solid electrolyte, such as step growth, chain growth, emulsion polymerization, solution polymerization, suspension polymerization, precipitation polymerization, and photopolymerization. Once the gel / solid electrolytes are formed by the polymerization steps, they may be assembled in a single battery housing as described herein. The battery may use a separator, or it may be membraneless or separatorless.

[0056]

[0067] As described herein, electrolytes may be polymerized or gelled to form polymer gel electrolytes (PGEs) for cathodeliand and / or anodeliand. The resulting PGE may be in a semi-solid state that resists flow within the battery. For example, a PGE may comprise an inert hydrophilic polymer matrix impregnated with an aqueous electrolyte. The electrolyte may be polymerized using any suitable technique. In one embodiment, a method for forming a PGE may begin with the selection of a monomer material for the PGE. The monomer may be a polar vinyl monomer selected from the group consisting of acrylic acid, vinyl acetate, acrylic acid esters, vinyl isocyanate, acrylonitrile, or any combination thereof. Subsequently, an aqueous electrolyte component may be selected and may comprise any of the above components relative to the electrolyte. An initiator may be added to initiate the polymerization process. In some embodiments, a crosslinking agent may be used in the electrolyte composition to further crosslink the polymer matrix to form the PGE. The monomer (e.g., polar vinyl monomer) in the composition may be present in an amount between approximately 5% and approximately 50% by weight, the initiator may be present in an amount between approximately 0.001% and approximately 0.1% by weight, and the crosslinking agent may be present in an amount between 0 and approximately 5% by weight.

[0057]

[0068] In some embodiments, the PGE may be formed in situ, which refers to introducing the electrolyte as a liquid into the housing and then polymerizing it to form the PGE within the housing. This method may allow the electrolyte composition to immerse itself in the voids, anode, and / or cathode before complete polymerization to form the PGE. In some embodiments, a vacuum (e.g., a pressure lower than atmospheric pressure) may be created within the housing 7 when introducing the electrolyte into the corresponding compartments. The vacuum may help remove air and allow the electrolyte to penetrate into the anode 13, the cathode 12, and / or various voids within the battery 10. In some embodiments, the vacuum may be between approximately 10 inches and 29.9 inches of mercury column, or between approximately 20 inches and 29.9 inches of vacuum mercury column. The use of a vacuum may help avoid the presence of air pockets within the battery 10 before complete polymerization of the electrolyte. In some embodiments, the electrodes may be immersed in the electrolyte for 1 to 120 minutes at a temperature between 0°C and 30°C before complete polymerization of the electrolyte to allow the electrolyte to impregnate the electrodes. Once the electrolyte is polymerized, the battery may be able to pause before use. In some embodiments, the battery may be able to pause for a period of time ranging from 5 minutes to 24 hours.

[0058]

[0069] To help impregnate the electrodes with the electrolyte, the electrodes may be pre-immersed in a selected electrolyte solution before the electrolyte is polymerized. This can be done by immersing the electrodes in an electrolyte outside the battery or housing (e.g., separately in the cathode or anode), and then placing the pre-immersed electrodes into the housing to construct the battery. In some embodiments, an electrolyte without polymers or gelling agents may be introduced into the battery to immerse the electrodes in place. This may involve the use of a vacuum to assist in electrode impregnation. The electrodes may be immersed for between approximately 1 minute and 24 hours. In some embodiments, immersion may be carried out over multiple cycles, in which the battery is filled with electrolyte, made immersable, drained, refilled, and made immersable again, drained a desired number of times. Once the electrodes are immersed and impregnated with the electrolyte, the electrolyte, including polymers and polymerizers (e.g., initiators, crosslinkers, etc.), may be introduced into the housing and made polymerizable to form the final battery.

[0059]

[0070] The electrolyte composition, monomer materials, initiators, and formation conditions (e.g., temperature) may be selected to provide a desired polymerization time that allows the electrolyte composition to properly immerse and absorb the battery components into the electrodes. Temperature may be controlled to regulate the polymerization process; lower temperatures may inhibit or slow polymerization, while higher temperatures may shorten or accelerate the polymerization process. Additionally, increasing the alkaline electrolyte component (e.g., hydroxide) may shorten the polymerization time, and increasing the initiator concentration will also shorten the polymerization time. A suitable polymerization time may range from 1 minute to 24 hours, based on the electrolyte solution composition and the reaction temperature.

[0060]

[0071] As an example of a polymerization process, a mixture of acrylic acid, N,N'-methylenebisacrylamide, and an alkaline solution can be produced at a temperature of about 0°C. Thereafter, any additives can be added to the solution (e.g., gas evolution inhibitors, additional additives as described herein). For example, zinc oxide, when used in an electrolyte, can be dissolved in the alkaline solution after mixing with the precursor components and may be beneficial during the electrochemical cycle of the anode. To polymerize the resulting mixture, an initiator such as potassium persulfate can be added to initiate the polymerization process and form a solid or semi-solid polymerized electrolyte (e.g., PGE). The resulting polymerized electrolyte may be stable over time once the polymerization process has occurred.

[0061]

[0072] As an example, the PGE described herein can be produced through a free radical polymerization process. In one embodiment, acrylic acid (AA) can be used as a monomer having N,N'-methylenebisacrylamide (MBA) as a crosslinking agent and potassium persulfate (K2S2O8) as an initiator. Alkaline electrolytes such as KOH may be added to this process and embedded in the framework. The addition of an alkaline electrolyte to AA results in neutralization, which reduces the concentration of the alkaline electrolyte in the polymer gel. Theoretical and experimental values ​​after neutralization of AA in KOH are reported in Figure 4. This plot is intended to serve as a guide for combining appropriate PGE concentrations for each electrode. Similarly, different concentrations of alkaline electrolytes can change the gelation time. Higher concentrations of alkaline electrolytes generally result in faster gelation, while lower concentrations of alkaline electrolytes result in longer gelation times. The initiator concentration can affect the gelation process. A thorough analysis of this process is reported in Figure 5 and also serves as a guide for producing PGE. The viscosity of the gel can be adjusted by changing the concentrations of monomers and MBA, which can also affect the ionic conductivity.

[0062]

[0073] The polymerization process may occur before the construction of the battery 10 or after the cells have been constructed. In some embodiments, the electrolyte may be polymerized and placed in a tray to form a sheet. Once polymerized, the sheet may be cut to the appropriate size and shape, and one or more layers may be used to form the electrolyte 15 that comes into contact with the anode 13. When using pre-formed PGE, additional liquid electrolyte may be introduced into the battery, and / or the electrodes may be pre-immersed in the electrolyte before the battery is constructed.

[0063]

[0074] In some embodiments, PGE can be formed using aqueous electrolytes, organic electrolytes, ionic liquids, aqueous electrolytes, etc. In some embodiments, the aqueous electrolyte can be used as the cathodelime and / or anodelime and gelled to form an aqueous hydrogel as PGE. In some embodiments, the aqueous hydrogel can be created through a free radical polymerization process. For example, acrylic acid (AA) can be selected as a monomer having N,N'-methylenebisacrylamide (MBA) as a crosslinking agent and potassium persulfate as an initiator. In aqueous alkaline batteries, a suitable hydroxide (e.g., potassium hydroxide (KOH), sodium hydroxide, lithium hydroxide, etc.) can be used to form the electrolyte. By neutralizing the hydroxide with AA, the hydroxide can be encapsulated in the hydrogel network. To create a hydrogel, the monomer can be combined with any crosslinking agent until the crosslinking agent is dissolved. Separately, a certain amount of hydroxide can be cooled to slow down the reaction. In some embodiments where the electrolyte is an aqueous electrolyte, the hydroxide can be cooled to a temperature below about 10°C, below about 5°C, or below about 0°C. Then, a mixed solution of monomer and any crosslinking agent can be added dropwise to a cooled hydroxide solution, as the neutralization reaction releases heat. An initiator, such as potassium persulfate, may be added to gel the resulting mixture of hydroxide, monomer, and crosslinking agent. The mixture can then be used to form a PGE. The amounts and concentrations of the components can be varied to obtain varying mechanical strengths of the hydrogel.

[0064]

[0075] Electrolytes containing ionic liquids may also be used to form PGE containing any of the ionic liquids described herein. To form PGE using an ionic liquid, a solution of any additives that may be contained in a suitable solvent may be prepared, and monomers may be added. The monomer may be any suitable monomer. For example, acrylamide may be used as a polymerizing agent for the ionic liquid. To this solution, the ionic liquid may be mixed together with the additive solution and an initiator. Any suitable initiator for use with the polymerizing agent may be used. For example, azobisisobutyronitrile may be used with acrylamide. The initiator may be added in a suitable amount, such as about 1% by weight of the polymerizing agent. This final solution may then be heated to form a polymerization gel.

[0065]

[0076] Organic electrolytes containing salts dissolved in organic solvents can also gel to form anodes and / or cathodes. As an example, lithium-ion conductive electrolytes can be gelled using several polymerization techniques, including ring-opening polymerization, photoinitiated radical polymerization, UV-initiated radical polymerization, thermal-initiated polymerization, in-situ polymerization, UV irradiation, and electrospinning. Lithium electrolytes may include lithium hexafluorophosphate (LiPF6), lithium perchlorate, bis(trifluoromethanesulfonyl)imide lithium, bis(oxalato)borate lithium, and combinations thereof in organic solvents such as ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate, ethylmethyl carbonate, and combinations thereof. An exemplary mixture is 1 M LiPF6 mixed in a solvent mixture of ethylene carbonate and dimethyl carbonate. Other solvents also exist that can be used as mixtures to reduce the flammability of organic electrolytes.

[0066]

[0077] Organic electrolytes can be gelled by mixing a selected salt with an organic solvent. A gelling agent may then be added together with an initiator. The gelling agent may be added in an amount between about 0.1% and about 5% by weight of the mixture, and the initiator may be added in an amount between about 0.01% and about 1% by weight of the mixture. In some embodiments, a suitable gelling agent for the organic electrolyte may include pentaerythritol tetraacrylate, and the initiator may include azodiisobutyronitrile. The resulting mixture can be gelled (e.g., polymerized) by heating the mixture to about 50–90°C, or about 70°C, and holding for 1–24 hours.

[0067]

[0078] For aqueous electrolytes that are essentially acidic or neutral, polymerization can be carried out using several processes. In one embodiment, a method for creating an acidic or neutral solid gelling aqueous electrolyte may involve adding acrylamide to a solution containing manganese sulfate, H2SO4, ammonium sulfate, potassium permanganate, and / or sulfuric acid. The gelling agent, including acrylamide, is added to the solution and may be mixed at a temperature between about 70 and 90°C for at least 1 hour until the solution is homogeneous. After the solution is thoroughly mixed, a crosslinking agent and an initiator may be added to the solution and mixed for 2 to 48 hours until the solution gels.

[0068]

[0079] In the final cell or battery design, a separator or buffer layer will be present to prevent mixing of the two PGEs, with a cathode having a lower PGE alkali concentration and an anode having a higher PGE alkali concentration. This final battery with a dual electrolyte allows for high electrode reversibility and improved or maximized utilization, and consequently, higher energy density.

[0069] Examples

[0080] Embodiments are described in general terms, and the following examples are given as specific embodiments of the present disclosure and to demonstrate their implementation and merits. It should be understood that the examples are given as examples and are not intended to limit the scope of the specification or claims in any way.

[0070] Example 1

[0081] The performance of a MnO2 cathode was tested at a low aqueous KOH concentration of 10 wt%. A cathode consisting of 80 wt% MnO2 (EMD), 15 wt% graphite, and 5 wt% Teflon was pressed against a nickel current collector. Sintered nickel was used as the counter electrode in the experiment. Zn was excluded as an anode in this experiment to eliminate its adverse effect on the performance of MnO2 in aqueous KOH. Cellophane was used as a separator. The cell potential was monitored and measured against a mercury / mercury oxide (Hg / HgO) reference electrode. The cathode was circulated using 40% of its theoretical capacity per electron (308 mAh / g).

[0071]

[0082] The performance of this cell is shown in Figure 6. Due to the low solubility of Mn ions, the cell circulates stably at low KOH concentrations. The cell does not show fade in terms of charge and discharge capacity per cycle. Although it shows a decrease in capacity fade after the cell potential reaches -0.4V relative to Hg|HgO, as can be seen in Figure 6, the cathode is able to provide its capacity of approximately 150mV beyond the voltage limit. -0.4V relative to Hg|HgO corresponds to approximately 1V relative to the zinc anode, which would be the end-discharge potential of a real battery. Similar cells with KOH concentrations exceeding 25 wt% will experience faster capacity fade due to the higher solubility of Mn ions.

[0072] Example 2

[0083] The cycling performance of a Zn mesh anode in high-concentration PGE was tested. PGE was prepared from 45 wt% KOH, which would become approximately 30 wt% after the gelation process, as shown in Figure 4. Zn mesh purchased from a commercial supplier was tested directly as a counter electrode in a cell with an oversized Zn anode. This oversized Zn anode also served as a reference within the cell. Cellophane was used as a separator. Figure 7 shows the cycling performance of the Zn mesh in high-concentration PGE. It can be seen that the performance of the Zn mesh is very stable in the gelled network.

[0073] Example 3

[0084] The complete discharge performance of a full MnO2|Zn cell was tested using a dual electrolyte design. A cathode consisting of 80 wt% MnO2(EMD), 15 wt% graphite, and 5 wt% Teflon was pressed against a nickel current collector. The MnO2 cathode was covered with PGE made with a low KOH concentration (20 wt%), and the Zn mesh anode was covered with PGE made with a high KOH concentration (50 wt%). Polyvinyl alcohol (PVA) was used as a separator. The cell was recycled to obtain maximum discharge performance. The performance is shown in Figure 8. It can be seen that the dual electrolyte cell was able to provide a capacity of 1e at the end of discharge.

[0074] Example 4

[0085] The cycling performance of a complete MnO2|Zn cell was tested using a dual electrolyte design. A cathode consisting of 80 wt% MnO2(EMD), 15 wt% graphite, and 5 wt% Teflon was pressed against a nickel current collector. The anode consisted of 95 wt% Zn powder (doped with bismuth and indium) and 5 wt% Teflon. The MnO2 cathode was covered with PGE made with a low KOH concentration (25 wt%), and the Zn mesh anode was covered with PGE made with a high KOH concentration (45 wt%). Polyvinyl alcohol (PVA) was used as a separator. The cycling performance of this cell is shown in Figure 9. It was designed to supply 40% of the one-electron capacity of MnO2. As can be seen from the performance, the cell was stably cyclable and was able to supply the designed capacity before the end of the cell voltage (1V).

[0075] Example 5

[0086] To enhance the performance of MnO2, the cycling capability of a complete MnO2|Zn cell was tested in a dual electrolyte design where the cathode PGE was expanded carbon embedded within the framework. The cathode, composed of 80 wt% MnO2(EMD), 15 wt% graphite, and 5 wt% Teflon, was pressed onto a nickel current collector. The anode was constructed of a Zn mesh. The MnO2 cathode was covered with a PGE made with a low KOH concentration (25 wt%), which had expanded graphite (BNB-90) embedded within its framework during the gelation process, while the Zn mesh anode was covered with a PGE made with a high KOH concentration (54 wt%). Polyvinyl alcohol (PVA) was used as a separator. The cycling performance of this cell is shown in Figure 10. It was designed to supply 40% of the MnO2's one-electron capacity. As the performance demonstrates, the cell was stably cyclable and capable of supplying the designed capacity before the end of the cell voltage (1V). Expanded graphite was incorporated into the framework to act as a capture source for any dissolved Mn ions. If the graphite dissolves away from the local electrode framework, it will act as a conductive framework for the PGE for Mn redeposit. After charging, this deposited Mn could be converted back to the 4+ state.

[0076] Example 6

[0087] The cycling performance of a complete MnO2|Zn cell was tested with a high-density cathode dual electrolyte design. The cathode, composed of 80 wt% MnO2(EMD), 15 wt% graphite, and 5 wt% Teflon, was pressed onto a nickel current collector. The anode was constructed of Zn mesh. The MnO2 cathode was covered with PGE made with a low KOH concentration (20 wt%), and the Zn mesh anode was covered with PGE made with a high KOH concentration (50 wt%). Polyvinyl alcohol (PVA) was used as a separator. The cycling performance of this cell is shown in Figure 11. It was designed to supply 40% of the one-electron capacity of MnO2. As can be seen from the performance, the cell was stably cyclable and was able to supply the designed capacity before the end of the cell voltage (1V). The high-density cathode and lower concentration of PGE helped improve the voltage behavior of the cell.

[0077]

[0088] This document describes various batteries, systems, and methods, and specific embodiments may include, but are not limited to, the following:

[0078]

[0089] In a first embodiment, the dual electrolyte battery comprises a cathode, an anode, a cathode liquid containing a first gelled electrolyte and in contact with the cathode, and an anodic liquid containing a second gelled electrolyte and in contact with the anode, wherein the concentration of the electrolyte in the anodic liquid is higher than the concentration of the electrolyte in the cathode liquid.

[0079]

[0090] A second embodiment may include the battery of the first embodiment, further comprising a separator disposed between the anode liquid and the cathode liquid.

[0080]

[0091] A third embodiment may include the battery of the first embodiment, further comprising a buffer layer disposed between the anode and the cathode, the buffer layer comprising a third gelled electrolyte.

[0081]

[0092] The fourth embodiment may include any one of the first to third embodiments, wherein the viscosity of the first gelled electrolyte is higher than the viscosity of the second gelled electrolyte.

[0082]

[0093] The fifth embodiment may include any one of the first to fourth embodiments, wherein the cathode includes an active material, and the active material is manganese oxide, lithium manganese oxide, aluminum manganese oxide, zinc manganese oxide, copper manganese oxide, bismuth manganese oxide, copper intercalated barnesite, copper intercalated bismuth barnesite, tin-doped manganese oxide, magnesium manganese oxide, silver oxide, silver dioxide, silver, nickel oxyhydroxide, nickel hydroxide, nickel, lead oxide, copper oxide, copper dioxide, lead, lead dioxide, potassium persulfate, sodium persulfate, ammonium persulfate, potassium permanganate, calcium permanganate, barium permanganate, silver permanganate, ammonium permanganate, peroxide, gold, perchlorate, cobalt oxide, ri The material comprises at least one of the following: thium cobalt oxide, sodium cobalt oxide, perchlorates, nickel oxides, bromine, mercury, vanadium oxide, bismuth vanadium oxide, hydroquinone, calix[4]quinone, tetrachlorobenzoquinone, 1,4-naphthoquinone, 9,10-anthraquinone, 1,2-naphthaquinone, 9,10-phenanthrenequinone, nitroxide-oxoammonium cation redox pairs such as 2,2,6,6-tetramethylpiperidine-1-yl)oxyl(TEMPO), carbon, 2,3-dicyano-5,6-dichlorodicyanoquinone, tetracyanoethylene, sulfur trioxide, ozone, oxygen, air, lithium nickel manganese cobalt oxide, sulfur, lithium iron phosphate, lithium copper oxide, lithium copper oxyphosphate, and any mixture thereof.

[0083]

[0094] The sixth embodiment may include any one of the first to fifth embodiments, wherein the cathode includes conductive carbon, and the conductive carbon includes graphite, carbon fiber, carbon black, acetylene black, single-walled carbon nanotubes, multi-walled carbon nanotubes, nickel or copper-coated carbon nanotubes, dispersions of single-walled carbon nanotubes, dispersions of multi-walled carbon nanotubes, graphene, graphene oxide, and combinations thereof.

[0084]

[0095] The seventh embodiment may include a battery as described in any one of the first to sixth embodiments, wherein the cathode includes a binder, and the binder includes polytetrafluoroethylene, carboxymethylcellulose, polyvinyl alcohol, or a combination thereof.

[0085]

[0096] The eighth embodiment may include any one of the first to seventh embodiments, wherein the cathode comprises 1 to 95% by weight of an active material, 4 to 98% by weight of conductive carbon, and 1 to 5% by weight of a binder.

[0086]

[0097] The ninth embodiment may include any one of the first to eighth embodiments, wherein the cathode comprises pressed cathode material on a current collector, and the current collector comprises carbon, lead, zinc, stainless steel, copper, nickel, silver, bismuth, titanium, magnesium, aluminum, indium, tin, gold, polypropylene, or a combination thereof.

[0087]

[0098] A tenth embodiment may include the battery of the ninth embodiment, wherein the current collector is a mesh, foil, foam, felt, fibrous, porous block structure, or a combination thereof.

[0088]

[0099] The eleventh embodiment may include a battery as described in any one of the first to tenth embodiments, wherein the anode includes an anode active material, and the anode active material includes zinc, aluminum, iron, copper, bismuth, tin, lithium, magnesium, calcium, titanium, or a combination thereof.

[0089]

[0100] The twelfth embodiment may include any one of the first to eleventh embodiments, wherein the anode comprises 90-100% active material and 0-10% binder.

[0090]

[0101] The 13th embodiment may include a battery as described in any one of the 1st to 12th embodiments, wherein the anode includes a binder, and the binder includes polytetrafluoroethylene, carboxymethylcellulose, polyvinyl alcohol, or a combination thereof.

[0091]

[0102] The 14th embodiment may include any one of the first to 13th embodiments, wherein the first gelled electrolyte includes an alkaline solution embedded in the gel, and the concentration of the alkaline solution is in the range of 1 to 25% by weight.

[0092]

[0103] The 15th embodiment may include any one of the first to 14th embodiments, wherein the second gelled electrolyte includes an alkaline solution embedded in the gel, and the concentration of the alkaline solution is in the range of 20 to 55% by weight.

[0093]

[0104] The sixteenth embodiment may include the battery described in any one of the first to fifteenth embodiments, wherein the alkaline solution includes potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, or a combination thereof.

[0094]

[0105] The 17th embodiment may include any one of the first to 16 embodiments, wherein the anode, cathode, or both include one or more electrolyte additives, the electrolyte additives include expanded graphite, carbon nanotubes, carbon black, graphene oxide, graphene, potassium carbonate, potassium fluoride, barium hydroxide, polytetrafluoroethylene, indium hydroxide, bismuth oxide, titanium oxide, cellulose fibers, or a combination thereof.

[0095]

[0106] The 18th embodiment may include any one of the first to 17 embodiments of a battery, further comprising at least one separator or buffer layer disposed between the anode liquid and the cathode liquid, wherein the at least one separator or buffer layer includes cellophane, Cellguard, polyvinyl alcohol, crosslinked polyvinyl alcohol, calcium hydroxide, polymer gel electrolyte, layered double hydroxide, NASICON, LISICON, or a combination thereof.

[0096]

[0107] In the 19th embodiment, the double electrolyte battery comprises a cathode, an anode, a cathode liquid containing a first gelled electrolyte and in contact with the cathode, and an anodic liquid containing a second gelled electrolyte and in contact with the anode, wherein the first gelled electrolyte and the second gelled electrolyte contain hydroxide, and the concentration of hydroxide in the anodic liquid is higher than the concentration of hydroxide in the cathode liquid.

[0097]

[0108] A 20th embodiment may include the battery of the 19th embodiment, further comprising a separator disposed between the anode liquid and the cathode liquid.

[0098]

[0109] The 21st embodiment may include a battery of the 19th or 20th embodiment, further comprising a buffer layer disposed between the anode and the cathode, the buffer layer comprising a third gelled electrolyte.

[0099]

[0110] The 22nd embodiment may include any one of the 19th to 21st embodiments, wherein the viscosity of the first gelled electrolyte is higher than the viscosity of the second gelled electrolyte.

[0100]

[0111] The 23rd embodiment may include any one of the 19th to 22nd embodiments, wherein the concentration of hydroxide in the first gelled electrolyte is in the range of 1 to 25% by weight.

[0101]

[0112] The 24th embodiment may include any one of the 19th to 23rd embodiments, wherein the concentration of hydroxide in the second gelled electrolyte is in the range of 20 to 55% by weight.

[0102]

[0113] The 25th embodiment may include any one of the fourth embodiments of the 19th to 21st embodiments, wherein the hydroxide includes potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, or a combination thereof.

[0103]

[0114] In the 26th embodiment, a method for forming a double electrolyte battery includes: placing a cathode containing a first gelled electrolyte in contact with a cathode; placing an anode containing a second gelled electrolyte, wherein the hydroxide concentration is higher than the hydroxide concentration in the cathode, in contact with an anode; and placing at least one separator or buffer layer between the anode and the cathode.

[0104]

[0115] The 27th aspect may include the method of the 26th aspect, further comprising arranging the cathode liquid, anode liquid, anode, and cathode in a housing to form a battery.

[0105]

[0116] The 28th aspect may include the method of the 26th or 27th aspect, wherein the buffer layer includes a third gelled electrolyte.

[0106]

[0117] The 29th embodiment may include the method according to any one of the 26th to 28th embodiments, wherein the viscosity of the first gelled electrolyte is higher than the viscosity of the second gelled electrolyte.

[0107]

[0118] The 30th embodiment may include the method according to any one of the 26th to 29th embodiments, wherein the concentration of hydroxide in the first gelled electrolyte is in the range of 1 to 25% by weight.

[0108]

[0119] The 31st embodiment may include the method according to any one of the 26th to 30th embodiments, wherein the concentration of hydroxide in the second gelled electrolyte is in the range of 20 to 55% by weight.

[0109]

[0120] The 32nd aspect may include the method described in any one of the 26th to 31st aspects, wherein the hydroxide includes potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, or a combination thereof.

[0110]

[0121] Embodiments are described herein with reference to the figures. However, since the systems and methods extend beyond their limited embodiments, it will be apparent to those skilled in the art that the detailed descriptions given herein with respect to those figures are for illustrative purposes only. For example, those skilled in the art will, of course, recognize numerous alternative and appropriate approaches in light of the teachings provided herein, depending on the needs of a particular application, and will implement any given detail function described herein beyond the selection of specific implementations in the embodiments described and shown below. That is, there are numerous modifications and variations, too many to list, but all within the scope of description herein. Also, singular forms should be interpreted as including plural forms and vice versa, masculine forms should be interpreted as including feminine forms and vice versa, and appropriate and alternative embodiments do not necessarily mean that the two are mutually exclusive.

[0111]

[0122] It should be further understood that the specific methodologies, compounds, materials, manufacturing techniques, uses, and applications described herein may vary, and that the descriptions herein are not limited to them. It should also be understood that the terms used herein are used solely for the purpose of describing specific embodiments and are not intended to limit the scope of the System and Method. It should be noted that, where used herein and in the appended claims (this application or any derivative application), the singular forms "a," "an," and "the" include plural references unless the context explicitly specifies otherwise. For example, a reference to "an element" refers to one or more elements, including their equivalents known to those skilled in the art. All conjunctions used should be understood in the most comprehensive sense possible. Therefore, the word "or" should be understood to have the definition of "logical OR" and not "exclusive OR" unless the context explicitly requires otherwise. It should also be understood that structures described herein may refer to functional equivalents of such structures. Language that can be interpreted as representing an approximation should be understood as such unless the context explicitly specifies otherwise.

[0112]

[0123] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those with ordinary skill in the art to which this description belongs. Any methods, techniques, devices, or materials similar or equivalent to those described herein may be used in carrying out or testing the System and Method, but preferred methods, techniques, devices, and materials are described. It should also be understood that structures described herein refer to functional equivalents of such structures. The System and Method are described in detail with reference to embodiments thereof, as shown in the accompanying drawings.

[0113]

[0124] Other variations and modifications will be apparent to those skilled in the art from the interpretation of this disclosure. Such variations and modifications may include equivalent and other features already known in the art and which may be used in place of or in addition to the features already described herein.

[0114]

[0125] While the claims may be formulated in this application or any further application derived therefrom for a particular combination of features, it should be understood that the scope of this disclosure also includes any novel features or any combination of novel features, or any generalization thereof, expressly or implicitly disclosed herein, regardless of whether they relate to the same system or method currently claimed in any of the claims and whether they mitigate some or all of the same technical problems as the system and method.

[0115]

[0126] Features described in the context of separate embodiments may be provided in combination in a single embodiment. Conversely, for the sake of brevity, various features described in the context of a single embodiment may be provided separately or in any suitable sub-combination. The applicant hereby informs that new claims may be formulated for such features and / or combinations of such features during the examination of this application or any further application derived therefrom.

Claims

1. MnO ２ A cathode containing, an anode containing Zn, A cathode solution comprising a first gelled electrolyte containing hydroxide, which comes into contact with the cathode, The system comprises a second gelled electrolyte containing hydroxide, and an anodic solution in contact with the anode, The second gelled electrolyte is in a semi-solid state that resists flow, and the hydroxide in the first gelled electrolyte and the hydroxide in the second gelled electrolyte are the same. The viscosity of the first gelled electrolyte is higher than the viscosity of the second gelled electrolyte. A dual electrolyte battery in which the concentration of the hydroxide electrolyte in the anode liquid is higher than the concentration of the hydroxide electrolyte in the cathode liquid.

2. The battery according to claim 1, further comprising a separator disposed between the anode liquid and the cathode liquid.

3. The system further comprises a buffer layer disposed between the anode liquid and the cathode liquid, The battery according to claim 1, wherein the buffer layer contains a third gelled electrolyte.

4. The cathode further comprises another active material, the active material being lithium manganese oxide, aluminum manganese oxide, zinc manganese oxide, copper manganese oxide, bismuth manganese oxide, copper intercalated barnesite, copper intercalated bismuth barnesite, tin-doped manganese oxide, magnesium manganese oxide, silver oxide, silver dioxide, silver, nickel oxyhydroxide, nickel hydroxide, nickel, lead oxide, copper oxide, copper dioxide, lead, lead dioxide, potassium persulfate, sodium persulfate, ammonium persulfate, potassium permanganate, calcium permanganate, barium permanganate, silver permanganate, ammonium permanganate, peroxide, gold, perchlorate, cobalt oxide, lithium cobalt oxide, sodium cobalt The battery according to claim 1, comprising at least one of oxides, perchlorates, nickel oxides, bromine, mercury, vanadium oxides, bismuth vanadium oxides, hydroquinones, calix[4]quinones, tetrachlorobenzoquinones, 1,4-naphthoquinones, 9,10-anthraquinones, 1,2-naphthaquinones, 9,10-phenanthrenequinones, nitroxide-oxoammonium cation redox pairs such as (2,2,6,6-tetramethylpiperidine-1-yl)oxyl (TEMPO), carbon, 2,3-dicyano-5,6-dichlorodicyanoquinones, tetracyanoethylenes, sulfur trioxides, ozone, oxygen, air, lithium nickel manganese cobalt oxide, sulfur, lithium iron phosphate, lithium copper oxide, lithium copper oxyphosphate, and any mixture thereof.

5. The battery according to claim 1, wherein the cathode further comprises conductive carbon, and the conductive carbon comprises graphite, carbon fiber, carbon black, acetylene black, single-walled carbon nanotubes, multi-walled carbon nanotubes, nickel or copper-coated carbon nanotubes, dispersions of single-walled carbon nanotubes, dispersions of multi-walled carbon nanotubes, graphene, graphene oxide, and combinations thereof.

6. The battery according to claim 1, wherein the cathode further comprises a binder, the binder comprising polytetrafluoroethylene, carboxymethylcellulose, polyvinyl alcohol, or a combination thereof.

7. The battery according to claim 1, wherein the cathode comprises 1 to 95% by weight of an active material, 4 to 98% by weight of conductive carbon, and 1 to 5% by weight of a binder.

8. The battery according to claim 1, wherein the cathode includes a pressed cathode material on a current collector, and the current collector includes carbon, lead, zinc, stainless steel, copper, nickel, silver, bismuth, titanium, magnesium, aluminum, indium, tin, gold, polypropylene, or a combination thereof.

9. The battery according to claim 8, wherein the current collector is a mesh, foil, foam, felt, fiber structure, porous block structure, or a combination thereof.

10. The battery according to claim 1, wherein the anode further comprises another anode active material, the anode active material comprising aluminum, iron, copper, bismuth, tin, lithium, magnesium, calcium, titanium, or a combination thereof.

11. The battery according to claim 1, wherein the anode comprises 90 to 100% active material and 0 to 10% binder.

12. The battery according to claim 1, wherein the anode comprises a binder, and the binder comprises polytetrafluoroethylene, carboxymethylcellulose, polyvinyl alcohol, or a combination thereof.

13. The battery according to claim 1, wherein the concentration of the hydroxide in the first gelled electrolyte is in the range of 1 to 25% by weight.

14. The battery according to claim 1, wherein the concentration of the hydroxide in the second gelled electrolyte is in the range of 20 to 55% by weight.

15. The battery according to claim 1, wherein the hydroxide comprises potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, or a combination thereof.

16. The battery according to claim 1, wherein the anode liquid, cathode liquid, or both contain one or more electrolyte additives, the electrolyte additives include expanded graphite, carbon nanotubes, carbon black, graphene oxide, graphene, potassium carbonate, potassium fluoride, barium hydroxide, polytetrafluoroethylene, indium hydroxide, bismuth oxide, titanium oxide, cellulose fibers, or a combination thereof.

17. The system further comprises at least one separator or buffer layer disposed between the anode liquid and the cathode liquid, The battery according to claim 1, wherein at least one of the separator or buffer layer comprises cellophane, a microporous separator, polyvinyl alcohol, crosslinked polyvinyl alcohol, calcium hydroxide, polymer gel electrolyte, layered double hydroxide, NASICON, LISICON, or a combination thereof.

18. MnO ２ Cathode and, Zn ammonium compounds, A cathode solution comprising a first gelled alkaline electrolyte and in contact with the cathode, The apparatus comprises a second gelled alkaline electrolyte and an anodic solution in contact with the anode, A double electrolyte battery wherein the first gelled alkaline electrolyte and the second gelled alkaline electrolyte contain hydroxide, the hydroxide in the first gelled alkaline electrolyte and the hydroxide in the second gelled alkaline electrolyte are the same, the viscosity of the first gelled alkaline electrolyte is higher than the viscosity of the second gelled alkaline electrolyte, and the concentration of the hydroxide in the anode liquid is higher than the concentration of the hydroxide in the cathode liquid.

19. The battery according to claim 18, further comprising a separator disposed between the anode liquid and the cathode liquid.

20. The system further comprises a buffer layer disposed between the anode liquid and the cathode liquid, The battery according to claim 18, wherein the buffer layer contains a third gelled alkaline electrolyte.

21. The battery according to claim 18, wherein the concentration of the hydroxide in the first gelled alkaline electrolyte is in the range of 1 to 25% by weight.

22. The battery according to claim 18, wherein the concentration of the hydroxide in the second gelled electrolyte is in the range of 20 to 55% by weight.

23. The battery according to claim 18, wherein the hydroxide comprises potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, or a combination thereof.

24. The cathode solution containing a first gelled electrolyte containing hydroxide is MnO ２ To be placed in contact with the cathode containing, The anode containing Zn is placed in contact with an anode, and the anode contains a second gelled electrolyte containing the same hydroxide as the hydroxide in the first gelled electrolyte, wherein the concentration of the hydroxide is higher than the concentration of the hydroxide in the cathode solution. This includes placing at least one separator or buffer layer between the anode liquid and the cathode liquid, A method for forming a double electrolyte battery, wherein the viscosity of the first gelled electrolyte is higher than the viscosity of the second gelled electrolyte.

25. The method according to claim 24, further comprising arranging the cathode liquid, anode liquid, anode, and cathode in a housing to form a battery.

26. The method according to claim 24, wherein the buffer layer comprises a third gelled electrolyte.

27. The method according to claim 24, wherein the concentration of the hydroxide in the first gelled electrolyte is in the range of 1 to 25% by weight.

28. The method according to claim 24, wherein the concentration of the hydroxide in the second gelled electrolyte is in the range of 20 to 55% by weight.

29. The method according to claim 24, wherein the hydroxide includes potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, or a combination thereof.

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