High voltage battery using gelled electrolyte

Abstract

The present application relates to a high-voltage aqueous battery comprising: a cathode comprising a cathode electroactive material, an anode comprising an anode electroactive material, a cathode electrolyte solution in contact with the cathode, and a polymeric anolyte solution in contact with the anode. The cathode electrolyte solution may be polymeric, and an optional separator may be used between the anolyte and cathode electrolytes.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of: 1) U.S. Provisional Application No. 62 / 867,959, filed on June 28, 2019, entitled “Membraneless High Voltage Aqueous Manganese Dioxide Batteries,” 2) U.S. Provisional Application No. 62 / 877,528, filed on July 23, 2019, entitled “High Voltage MnO2|Zn and MnO2|Al Batteries Using Permanganate and Gelated Alkaline Electrolytes,” and 3) U.S. Provisional Application No. 62 / 895,706, filed on September 4, 2019, entitled “All-Solid-State High Voltage Aqueous Batteries with High Ionic Conductivity,” all of which are incorporated herein by reference in their entirety.

[0003] Statement Regarding Government-Sponsored Research or Development

[0004] not applicable. Background Art

[0005] Aqueous batteries containing manganese dioxide as the cathode active material are ubiquitous in the modern world. Paired with a zinc anode, they are widely marketed as primary batteries for use in household electronics, camera batteries, video game controller batteries, and more. Due to their alkaline electrolytes, these batteries typically have an open-circuit potential of 1.5 to 1.6 V. Batteries containing acidic or neutral electrolytes, marketed as Leclanche batteries, have open-circuit potentials in a similar range to alkaline batteries.

[0006] There are other batteries that can compete with aqueous batteries. For example, lithium (Li)-ion batteries dominate the storage space in almost all types of applications. Li-ion batteries also appear to have reached their practical insertion limit, so the energy density of these batteries will not increase much further. Summary of the Invention

[0007] In some embodiments, a high voltage aqueous battery comprises: a cathode comprising a cathode electroactive material, an anode comprising an anode electroactive material, a cathode electrolyte solution in contact with the cathode, and a polymeric anolyte solution in contact with the anode. The cathode electrolyte solution can be polymeric, and an optional separator can be used between the anolyte and cathode electrolytes.

[0008] In some embodiments, a high voltage aqueous battery comprises: a cathode comprising manganese dioxide, spinel manganese oxide (Mn3O4) or manganese oxide (MnO), an anode comprising zinc, aluminum, magnesium or iron, a polymeric cathode electrolyte solution in contact with the cathode, and a polymeric anode electrolyte solution in contact with the anode.

[0009] In some embodiments, a high voltage aqueous battery comprises: a cathode comprising lead oxide (PbO2), an anode comprising zinc, aluminum, magnesium, or iron, a polymeric cathode electrolyte solution in contact with the cathode, and a polymeric anolyte solution in contact with the anode.

[0010]

[0011] These and other features will become more clearly understood from the following detailed description taken in conjunction with the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] A more complete understanding of the present application and its advantages will now be obtained by referring to the brief description and detailed description taken in conjunction with the accompanying drawings, wherein like reference numerals represent like parts.

[0012] Figure 1 is a schematic cross-sectional view of a battery according to some embodiments.

[0013] Figure 2 is a perspective view of an electrode of a cylindrical battery or a jelly roll battery according to some embodiments.

[0014] Figure 3 is another schematic cross-sectional view of a battery according to some embodiments.

[0015] Figure 4 is another schematic cross-sectional view of a battery according to some embodiments.

[0016] Figure 5 is another schematic cross-sectional view of a battery according to some embodiments.

[0017] Figure 6 Shown is a graph of potential versus time for a test cell as described in Example 1 using zinc as the anode.

[0018] Figure 7 Shown is a graph of capacity versus cycle number for cells tested as described in Example 1.

[0019] Figure 8 The coulombic efficiency and energy efficiency of the cells tested as described in Example 1 are shown.

[0020] Figure 9 A plot of potential versus time for a test cell as described in Example 2 is shown.

[0021] Figure 10 A graph of the first discharge potential of a cell tested as described in Example 3 is shown.

[0022] Figure 11 A graph showing the open circuit potential of three cells with different electrolytes as described in Example 4 is shown.

[0023] Figure 12 The first three discharge cycles of three cells with different electrolytes as described in Example 4 are shown.

[0024] Figure 13 The cycle life of a manganese dioxide battery using permanganate as described in Example 4 is shown.

[0025] Figure 14 Shown is a graph of potential versus discharge capacity for cells tested as described in Example 5.

[0026] Figure 15 The cycling curve of the manganese dioxide battery as described in Example 6 is shown.

[0027] Figure 16 Shown is an SEM image of the charged electrode as described in Example 6, showing the deposition of manganese dioxide.

[0028] Figure 17 Shown is the X-ray diffraction pattern of a cathode containing manganese dioxide at the end of a charging cycle as described in Example 6.

[0029] Figure 18 Schematically showing a graph of voltage versus capacity for various technologies.

[0030] Figure 19 Shown are images of gelled manganese sulfate with sulfuric acid and various additives and a picture of gelled potassium hydroxide with zinc mesh as described in Example 7 (lower left image).

[0031] Figure 20 The open circuit potential of the cells tested as described in Example 8 is shown.

[0032] Figure 21 Shown are the discharge curves of three test cells as described in Example 8.

[0033] Figure 22 The cycling performance of the cells tested as described in Example 8 is shown.

[0034] Figure 23 The open circuit potential of the cells tested as described in Example 9 is shown.

[0035] Figure 24 Shown is the discharge curve of a test cell without a membrane as described in Example 9.

[0036] Figure 25 The cycling performance of the membrane-free test cell as described in Example 9 is shown. DETAILED DESCRIPTION

[0037] In this application, the terms "negative electrode" and "anode" are both used to refer to a "negative electrode". Similarly, the terms "positive electrode" and "cathode" are both used to refer to a "positive electrode". Reference to an "electrode" alone may refer to an anode, a cathode, or both. Reference to the term "primary cell" (e.g., "primary cell," "primary electrochemical cell," or "primary battery") refers to a cell or battery that is disposed of and replaced after a single discharge. Reference to the term "secondary cell" (e.g., "secondary cell," "secondary electrochemical cell," or "secondary battery") refers to a cell or battery that can be recharged one or more times and reused. As used herein, a cathode electrolyte refers to an electrolyte solution that is in contact with the cathode but not in direct contact with the anode, and an "anode electrolyte" refers to an electrolyte solution that is in contact with the anode but not in direct contact with the cathode.

[0038] Alkaline batteries are widely used due to their superior storage properties and high ionic conductivity compared to acidic or neutral electrolytes. However, these batteries can only be used once and then discarded due to the deactivation of their raw materials. In addition, the energy extracted from these batteries deteriorates during use, as the nominal voltage at which capacity is extracted is approximately 1.1 to 1.2 V. These characteristics limit the use of this inexpensive, safe, non-flammable, and environmentally friendly chemistry to small-scale applications. If the battery voltage can be increased, a high proportion of the theoretical capacity of the raw materials can be reversibly obtained multiple times. If the cost of the battery can be maintained at a low level, it will represent a major advancement in the field of energy storage systems, as it will open up the use of manganese dioxide-zinc batteries in applications that have a large impact on human life, such as grid storage applications, home backup power, and use in mobile electronics.

[0039] In some embodiments, a high voltage aqueous battery is disclosed in which manganese oxide (MnO2) and, in some embodiments, lead oxide (PbO2) are the primary cathode active materials. The anode of the high voltage battery can be zinc (Zn), aluminum (Al), magnesium (Mg) and / or iron (Fe) active materials. The high voltage in the battery can be achieved by maintaining different pH in the cathode and anode compartments of the battery, where the cathode is typically in an acidic to neutral solution, while the anode can be in an alkaline solution. In some embodiments, the innovative high voltage aspect can be achieved by polymerizing an alkaline electrolyte on the anode side and using an electrolyte containing permanganate on the cathode side. The resulting battery can be a stationary high voltage (2.8-4V) membraneless aqueous battery containing manganese dioxide as the cathode. The battery also does not require flow or flow-assisted conditions. The manganese dioxide disclosed in this patent application can reach 80% to 100% of its single electron (308mAh / g) and two electron (617mAh / g) capacities, respectively.

[0040] In some embodiments, the battery can be a fully solid-state, high-voltage aqueous battery that can deliver energy at a higher voltage than any battery currently available on the market. In this embodiment, the cathode can contain manganese dioxide (MnO2) or lead oxide (PbO2) as the cathode active material, and the anode can contain zinc (Zn), aluminum (Al), magnesium (Mg) and / or iron (Fe) as the anode active material. The high voltage of this battery can be achieved by maintaining the cathode and anode compartments of the battery at different pHs, where the cathode is typically in an acidic to neutral solution and the anode is in an alkaline / basic solution. The fully solid-state aspect can be achieved by polymerizing the cathode electrolyte and the anode electrolyte. Gelation of the electrolyte can lead to a decrease in ionic conductivity, which can be compensated by increasing the ionic conductivity of the system by adding ammonium salts to the cathode electrolyte and potassium salts to the anode electrolyte. Better voltage characteristics can also be obtained by using additional dopants on the cathode electrode and / or the electrolyte. This is the first disclosure of all-solid-state MnO2|Zn, MnO2|Al, MnO2|Mg, and MnO2|Fe and PbO2|Zn, PbO2|Al, PbO2|Mg, and PbO2|Fe high-voltage aqueous batteries (HiVABs), where the potential of the MnO2|Zn system is between 2.5 and 4 V, and the potential of the PbO2|Zn system is ~3 V. The manganese dioxide disclosed in this patent application can achieve 80% to 100% of its one-electron (308 mAh / g) and two-electron (617 mAh / g) capacities, respectively. Other forms of manganese oxides, such as spinel manganese oxides (Mn3O4, LiMn2O4 and / or ZnMn2O4) and manganese oxide (MnO) can also be used as cathodes.

[0041] In some embodiments, a high voltage aqueous manganese dioxide battery is provided that can reach its theoretical single electron (308 mAh / g) and two electron (617 mAh / g) capacity. The high voltage can be achieved by creating a dual electrolyte battery, in which the cathode is in an acidic or nearly neutral electrolyte and the anode is in an alkaline electrolyte. The battery can be constructed in several different ways. In some embodiments, the cathode can have a liquid cathode electrolyte consisting of an acidic or neutral solution, and the anode can be in contact with an anode electrolyte, which is a polymerized or gelled electrolyte. For this type of battery, a separator is optionally used, and in some embodiments, there is no separator between the cathode electrolyte and the anode electrolyte. In some embodiments, the battery can include a liquid cathode electrolyte and a polymerized or gelled anode electrolyte, and a separator disposed between the cathode electrolyte and the anode electrolyte. In some embodiments, both the cathode electrolyte and the anode electrolyte can be polymerized or gelled, and no separator can be disposed between the cathode electrolyte and the anode electrolyte. In other embodiments, both the cathode electrolyte and the anode electrolyte can be polymerized or gelled, and a separator can be disposed between the cathode electrolyte and the anode electrolyte. Each of these embodiments is described in more detail herein.

[0042] refer to Figure 1 , the battery 10 may have a housing 7, a cathode 12, and an anode 13, wherein the cathode 12 may include a cathode current collector 1 and a cathode material 2. In some embodiments, the anode 13 may include an anode current collector 4 and an anode material 5. It should be noted that, Figure 1 The components may not be accurately scaled as these features are shown to clearly illustrate the electrolyte surrounding the anode 13 and cathode 12 . Figure 1 A prismatic cell arrangement is shown with a single anode 13 and cathode 12. In another embodiment, the cell may be a cylindrical cell with concentrically arranged electrodes (e.g., as Figure 2 ), or a wound structure in which the anode and cathode are layered and then wound in a roll-type structure. The cathode current collector 1 and the cathode material 2 are collectively referred to as the cathode 12 or the positive electrode 12, as shown. Figure 2 . Similarly, the anode material 5 with the optional anode current collector 4 can be collectively referred to as the anode 13 or negative electrode 13. The cathode electrolyte 3 can be in contact with the cathode 12, and the anolyte 6 can be in contact with the anode 13. As described in more detail herein, the cathode electrolyte 3 and / or the anolyte 6 can be polymerized or gelled to prevent mixing between the two electrolyte solutions.

[0043] In some embodiments, the battery 10 may include one or more cathodes 12 and one or more anodes 13. When there are multiple anodes 13 and / or multiple cathodes 12, the electrodes may be configured as a layered structure in which the electrodes alternate (e.g., anode, cathode, anode, etc.). Any number of anodes 13 and / or cathodes 12 may be present to provide the desired capacity and / or output voltage. In a jellyroll configuration, the battery 10 may have only one cathode 12 and one anode 13 wound in a jellyroll configuration, such that a cross-section of the battery 10 includes a layered structure of alternating electrodes.

[0044] In one embodiment, housing 7 comprises a molded case or container that is generally non-reactive with the electrolyte solution in battery 10, wherein the electrolyte solution comprises cathode electrolyte 3 and anode electrolyte 6. In one embodiment, housing 7 comprises a polypropylene molded case, an acrylic polymer molded case, or the like.

[0045] The cathode 12 can include a mixture of multiple components, including an electrochemically active material, a binder, a conductive material, and / or one or more additional components that can be used to improve the life, rechargeability, and electrochemical performance of the cathode 12. The cathode can include an active cathode material 2 (e.g., an electroactive material). Suitable cathode materials 2 can include, but are not limited to, manganese dioxide, copper manganese oxide, manganese oxide, copper-intercalated bismuth birnessite, birnessite, todokorite, manganese ore, pyrolusite, rhodochrosite, lead, lead hydroxide, lead oxide, or any combination thereof. The electroactive component in the cathode material 2 can be between 1 and 99 wt.%, based on the weight of the cathode material 2, and the conductive additive can be between 1 and 99 wt.%.

[0046] In some embodiments, the active cathode material can be based on one or more polymorphs of manganese dioxide, including electrolytic manganese dioxide (EMD), α-MnO 2 , β-MnO 2 , γ-MnO 2 , δ-MnO 2 , ε-MnO 2 , or λ-MnO 2. Other forms of manganese dioxide may also be present, such as pyrolusite, birnessite, dactylinite, ramsonite, philomena, todorkite, tremolite, chalcopyrite, sodium- or potassium-rich birnessite, cryptomanganite, ferrierite, manganese oxyhydroxide (MnOOH), α-MnOOH, γ-MnOOH, β-MnOOH, manganese hydroxide [Mn(OH) 2], partially or fully protonated manganese dioxide, Mn 3 O 4 , Mn 2 O 3 , bixbyite, MnO, lithiated manganese dioxide (LiMn 2 O 4 ), CuMn 2 O 4 , zinc manganese dioxide, or any combination thereof. Generally, the circulating form of manganese dioxide in the cathode can have a layered structure, which in some embodiments can include delta-MnO2, which is interchangeably referred to as birnessite. If non-birnessite polymorphs of manganese dioxide are used, these can be converted to birnessite in situ through one or more conditioning cycles, as described in more detail below. For example, a full or partial discharge to the end of the second electron stage of the manganese dioxide (e.g., between about 20% and about 100% of the second electron capacity of the cathode) can be performed and then recharged back to its MnO2 state. 4+ state, thereby producing birnessite phase manganese dioxide.

[0047] The addition of conductive additives (such as conductive carbon) enables high volume and weight energy density to be obtained in the cathode material with high load of electroactive material. The conductive additive can be present in a concentration of about 1wt.% to 30wt.%. 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 a combination thereof. In some embodiments, higher electroactive material loads in the cathode are ideal for increasing 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 (examples, KS15, KS44, KC44, MB15, MB25, MK15, MK25, MK44, MX15, MX25, BNB90, LB series) TIMREX dispersions; ENASCO 150G, 210G, 250G, 260G, 350G, 150P, 250P; SUPER P, SUPER P Li, carbon black (examples include Ketjenblack EC-300J, Ketjenblack EC-600JD, Ketjenblack EC-600JD powder), acetylene black, carbon nanotubes (single-wall or multi-wall), Zenyatta graphite, and combinations thereof. When the electroactive material includes manganese, the birnessite discharge reaction includes a dissolution-precipitation reaction, wherein Mn 3+ ions become soluble and form Mn 2+ This second electron process can involve the formation of a non-conductive manganese hydroxide [Mn(OH)2] layer on the conductive graphite.

[0048] In some embodiments, the conductive additive may have a particle size range of about 1 to about 50 microns, or about 2 to about 30 microns, or about 5 to about 15 microns. In one embodiment, the conductive additive may include expanded graphite having a particle size range of about 10 to about 50 microns, or about 20 to about 30 microns. In some embodiments, the mass ratio of graphite to conductive additive may be in the range of about 5:1 to about 50:1, or about 7:1 to about 28:1. The total carbon mass percentage in the cathode paste may be in the range of about 5% to about 99%, or about 10% to about 80%. In some embodiments, the electroactive component in the cathode material 2 may be between 1 wt.% and 99 wt.% of the weight of the cathode material 2, and the conductive additive may be between 1 and 99 wt.%.

[0049] The cathode material 2 may also include a conductive component. Adding a conductive component (such as a metal additive) to the cathode material can be achieved by adding one or more metal powders (such as nickel powder) to the cathode mixture. The conductive metal component may be present in a concentration of about 0 wt.% to 30 wt.%. 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 in the form of an oxide and / or a 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 serve as a supporting conductive skeleton for the first and second electronic reactions to occur. The second electronic reaction has a dissolution-precipitation reaction, in which Mn 3+ The ions become soluble in the electrolyte and precipitate on the graphite, resulting in an electrochemical reaction and the formation of non-conductive manganese hydroxide [Mn(OH)2]. This ultimately leads to capacity fading in subsequent cycles. Suitable second components include transition metals such as nickel, cobalt, iron, titanium, and metals such as silver, gold, aluminum, and calcium. Oxides and salts of these metals are also suitable. Transition metals such as cobalt also help reduce the Mn 3+ The conductive metal components can be incorporated into the electrode by chemical or physical methods (e.g., ball milling, mortar / pestle, spex mixture). An example of such an electrode includes 5% to 95% birnessite, 5% to 95% conductive carbon, 0% to 50% of the second conductive metal component, and 1% to 10% of a binder.

[0050] In some embodiments, a binder can be used with the cathode material 2. The binder can be present in a concentration of about 0 wt.% to 10 wt.%. In some embodiments, the binder includes a water-soluble cellulose-based hydrogel, which can be used as a thickener and a strong binder and has been cross-linked with a conductive polymer with good mechanical strength. The binder can also be a cellulose film sold as cellophane. The binder can be prepared by physically cross-linking the water-soluble cellulose-based hydrogel with the polymer through repeated cooling and thawing cycles. In some embodiments, the binder can include a 0 wt.% to 10 wt.% carboxymethyl cellulose (CMC) solution cross-linked with an equal volume of 0 wt.% to 10 wt.% polyvinyl alcohol (PVA). Compared to the conventional use In comparison, the adhesive showed excellent performance. It is a very resistive material, but is widely used in industry due to its good rollability. However, this does not exclude the use of As an adhesive.

[0051] A mixture of a water-based binder and some conductive carbon is used to make a rollable adhesive. Using a water-based binder helps achieve most of the two-electron capacity with minimal capacity loss over multiple cycles. In some embodiments, the adhesive can be water-based, which has excellent water retention, adhesive properties, and relative to using The same cathode of the binder helps to maintain conductivity. Examples of hydrogels may include, but are not limited to, methylcellulose (MC), carboxymethylcellulose (CMC), hydroxypropylcellulose (HPH), hydroxypropylmethylcellulose (HPMC), hydroxyethylmethylcellulose (HEMC), carboxymethylhydroxyethylcellulose and hydroxyethylcellulose (HEC). Examples of cross-linked polymers include polyvinyl alcohol, polyvinyl acetate, polyaniline, polyvinylpyrrolidone, polyvinylidene fluoride and polypyrrole. In some embodiments, 0 wt.% to 10 wt.% aqueous cellulose hydrogen solution is cross-linked with 0 wt.% to 10 wt.% cross-linked polymer solution by, for example, repeated freeze / thaw cycles, radiation treatment or chemical reagents (such as epichlorohydrin). The aqueous binder can be cross-linked with 0% to 5% of Mixed to improve manufacturability.

[0052] The cathode material 2 may also contain additional elements. Additional elements, including bismuth compounds and / or copper / copper compounds, may be included in the cathode material to collectively improve the cathode's galvanostatic battery cycling. When present as birnessite, the copper and / or bismuth may be incorporated into the birnessite's layered nanostructure. Because copper and bismuth are incorporated into the birnessite's crystals and nanostructure, the resulting birnessite cathode material may exhibit improved cycling and long-term performance.

[0053] The bismuth compound can be incorporated into cathode 12 in the form of an inorganic or organic salt of bismuth (oxidation state 5, 4, 3, 2, or 1), bismuth oxide, or bismuth metal (i.e., elemental bismuth). The bismuth compound can be present in the cathode material at a concentration of about 1 wt.% to 20 wt.% based on the weight of the cathode material 2. Examples of inorganic 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 oxynitrate, bismuth gallate hydrate, bismuth phosphate, bismuth cobalt zinc oxide, bismuth sulfite agar, bismuth oxychloride, bismuth aluminate hydrate, bismuth tungsten oxide, bismuth lead strontium calcium copper oxide, bismuth antimonide, bismuth antimony telluride, stabilized bismuth oxide yittia, bismuth-lead alloy, ammonium bismuth citrate, 2-naphthol bismuth salt, dichloritri(o-tolyl)bismuth, dichlorodiphenyl(p-tolyl)bismuth, triphenylbismuth, or any combination thereof.

[0054] The copper compound can be incorporated into the cathode 12 in the form of an organic or inorganic salt of copper (oxidation state 1, 2, 3 or 4), copper oxide or copper metal (i.e., elemental copper). The copper compound can be present in a concentration of about 1 wt.% to 70 wt.% of the weight of the cathode material 2. In some embodiments, the copper compound is present in a concentration of about 5 wt.% to 50 wt.% of the weight of the cathode material 2. In other embodiments, the copper compound is present in a concentration of about 10 wt.% to 50 wt.% of the weight of the cathode material 2. In yet another embodiment, the copper compound is present in a concentration of about 5 wt.% to 20 wt.% of the weight of the cathode material 2. Examples of copper compounds include: copper and copper salts, such as copper aluminum oxide, copper (I) oxide, copper (II) oxide and / or copper salts in the +1, +2, +3 or +4 oxidation states, including but not limited to copper nitrate, copper sulfate, copper chloride, etc. The role of copper is to change the oxidation and reduction voltages of bismuth. This enables the cathode to be fully reversible during galvanostatic cycling, compared to bismuth-modified manganese dioxide, which cannot withstand galvanostatic cycling.

[0055] The cathode 12 can be produced using a method that can be implemented in large-scale manufacturing. For a MnO2 cathode, the cathode 12 is capable of delivering the entire second electron capacity of the MnO2. Both low and high loadings of MnO2 in the mixed material can achieve excellent rechargeability, thereby enabling the battery / battery to achieve a very high practical energy density. In some embodiments, the cathode material may include 2 wt.% to 30 wt.% conductive carbon, 0 wt.% to 30 wt.% conductive metal additives, 1 wt.% to 70 wt.% copper compounds, 1 wt.% to 20 wt.% bismuth compounds, 0 wt.% to 10 wt.% binder, and birnessite or EMD. In another embodiment, the cathode material includes 2 wt.% to 30 wt.% conductive carbon, 0 wt.% to 30 wt.% conductive metal additives, 1 wt.% to 20 wt.% bismuth compounds, 0 wt.% to 10 wt.% binder, and birnessite or EMD. In one embodiment, the cathode material consists essentially of 2 to 30 wt.% conductive carbon, 0 to 30 wt.% conductive metal additive, 1 to 70 wt.% copper compound, 1 to 20 wt.% bismuth compound, 0 to 10 wt.% binder, and the balance is birnessite or EMD. In another embodiment, the cathode material consists essentially of 2 to 30 wt.% conductive carbon, 0 to 30 wt.% conductive metal additive, 1 to 20 wt.% bismuth compound, 0 to 10 wt.% binder, and the balance is birnessite or EMD.

[0056] The porosity of the resulting cathode can range from 20% to 85% as measured by mercury penetration porosimetry.Porosity can be measured according to ASTM D4284-12 "Standard Test Method for Pore Volume Distribution of Catalysts and Catalyst Supports by Mercury Intrusion Porosimetry."

[0057] The cathode material 2 can be formed on a cathode current collector 1 formed of a conductive material, wherein the conductive material serves as an electrical connection between the cathode material and one or more external electrical connections. In some embodiments, the cathode current collector 1 can be, for example, carbon, lead, nickel, steel (e.g., stainless steel, etc.), 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 can form a mesh (e.g., an expanded mesh, a woven mesh, etc.), a perforated metal, a foam, a foil, a felt, a fiber, a porous block structure, a perforated foil, a wire mesh, a wrapped assembly, or any combination thereof. In some embodiments, the current collector can form a bag assembly or form part of a bag assembly, wherein the pocket can hold the cathode material 2 within the current collector 1. A tab (e.g., a portion of the cathode current collector 1 that extends to the outside of the cathode material 2, such as Figure 1 The top of the cathode 12 (shown) can be connected to a current collector to provide an electrical connection between an external power source and the current collector.

[0058] The cathode material 2 may be pressed onto the cathode current collector 1 to form the cathode 12. For example, the pressure may be between 1000 psi and 20000 psi (6.9×10 6 and 1.4×10 8 The cathode material 2 is adhered to the cathode current collector 1 by pressing under a pressure of between 100 and 150 Pascals. The cathode material 2 may be adhered to the cathode current collector 1 in the form of a paste. When a tab of the cathode current collector 1 is present, it may extend to the outside of the housing 7 to form a current collector tab.

[0059] The cathode electrolyte 3 may be disposed in the housing 10 in contact with the cathode material 2 and the anode electrolyte 6. Figure 1 In the embodiment shown, the anolyte 6 may be polymerized or gelled, and the catholyte 3 may be liquid. Even when the catholyte 3 is liquid, the polymerization of the anolyte 6 may prevent mixing between the catholyte 3 and the anolyte 6.

[0060] In some embodiments, the cathode electrolyte may include an acid, such as an inorganic acid (e.g., hydrochloric acid, nitric acid, sulfuric acid, etc.). For acidic cathode electrolyte compositions, the acid concentration may be between about 0 M and about 16 M. In some embodiments, the cathode electrolyte solution may include potassium permanganate, sodium permanganate, lithium permanganate, calcium permanganate, manganese sulfate, manganese chloride, manganese nitrate, manganese perchlorate, manganese acetate, manganese bis(trifluoromethanesulfonate), manganese trifluoromethanesulfonate, manganese carbonate, manganese oxalate, manganese fluorosilicate, manganese ferrocyanide, manganese bromide, magnesium sulfate, zinc sulfate, zinc trifluoromethanesulfonate, zinc acetate, zinc nitrate, bismuth chloride, bismuth nitrate, nitric acid, sulfuric acid, hydrochloric acid, sodium sulfate, potassium 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, or any combination thereof. For example, the cathode solution may include manganese sulfate mixed with sulfuric acid or potassium permanganate mixed with sulfuric acid. Other dopants of the solution may include zinc sulfate, lead sulfate, titanium disulfide, titanium sulfate hydrate, silver sulfate, cobalt sulfate, and nickel sulfate. The cathode electrolyte may be an acidic or neutral solution, and the pH of the cathode electrolyte may be between -1.2 and 7. The cathode electrolyte may be used at temperatures between 0 and 200°C.

[0061] In some embodiments, the cathode electrolyte may include permanganate. Permanganate has a relatively high positive potential. This enables an increase in the overall cell potential within the battery 10. When permanganate is present, it may be present in a molar ratio of acid (e.g., an inorganic acid such as hydrochloric acid, sulfuric acid, etc.) to permanganate of about 1:1 to about 1:6, or about 1:2 to about 1:4, or about 1:3, although the exact amount may vary based on the expected operating conditions of the battery 10. The concentration of permanganate (e.g., potassium permanganate or a salt of permanganate, etc.) may be greater than 0 and less than or equal to 5M. In some embodiments, the cathode electrolyte solution comprises sulfuric acid, hydrochloric acid, or nitric acid at a concentration greater than 0 and less than or equal to 16M. The use of permanganate is advantageous for making high-voltage batteries, such that when a cathode electrolyte having permanganate is used in combination with a very negative anode potential, the resulting battery can have a voltage of approximately 2.8V when the cathode and anode are MnO2|Zn, and a voltage of approximately 4V when the cathode and anode are MnO2|Al.

[0062] In some embodiments, the electroactive component of the anode material 5 may include zinc, aluminum, magnesium, iron, or any combination thereof. In some embodiments, the anode material 5 may include iron oxide, iron hydroxide, bismuth oxide, bismuth, indium oxide, indium hydroxide, indium, copper, copper oxide, copper hydroxide, manganese oxide (e.g., Mn3O4, Mn2O3, MnO2, combinations thereof, etc.), or a combination thereof. In an alkaline electrolyte, the anode material 5 may have a relatively negative reduction potential, which allows the voltage in the battery to be relatively high. When manganese dioxide is in an acidic solution and the anode material 5 includes zinc or aluminum in contact with an alkaline solution, a cell voltage of >2.4-4V can be achieved, which makes the battery equivalent to or better than those of lithium ion, lithium metal, sodium ion, sodium metal, potassium ion, potassium metal, calcium ion, calcium metal, magnesium metal, and metal-sulfur chemistry, which are generally flammable, toxic, and very expensive.

[0063] In some embodiments, the anode material 5 may include zinc, which may be present in the form of elemental zinc and / or zinc oxide. In some embodiments, the zinc anode mixture includes zinc, zinc oxide (ZnO), a conductive material, and a binder. In the anode material 5, zinc may be present in an amount of about 50 wt.% to about 90 wt.%, or about 60 wt.% to about 80 wt.%, or about 65 wt.% to about 75 wt.%, based on the total weight of the anode material. In addition to or in place of zinc, additional elements that may be present in the anode include, but are not limited to, lithium, aluminum, magnesium, iron, cadmium, or any combination thereof, each of which may be present in the same or similar amount as the zinc described herein.

[0064] In some embodiments, the anode material 5 may include zinc oxide (ZnO), which may be present in an amount of about 5 wt.% to about 20 wt.%, or about 5 wt.% to about 15 wt.%, or about 5 wt.% to about 10 wt.%, based on the total weight of the anode material. As will be understood by those skilled in the art and with the aid of 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 charge and discharge phases.

[0065] In one embodiment, the conductive material may optionally be present in the anode material in an amount of about 5 wt.% to about 20 wt.%, or about 5 wt.% to about 15 wt.%, or about 5 wt.% to about 10 wt.%, based on the total weight of the anode material. As will be understood by those skilled in the art and with the aid of the present disclosure, the conductive material may be used as a conductive agent in the zinc anode mixture, for example to enhance the overall conductivity of the Zn anode mixture. Non-limiting examples of conductive materials suitable for use may include any conductive carbon described herein, such as carbon, graphite, graphite powder, graphite flakes, graphite powder spheres, carbon black, activated carbon, conductive carbon, amorphous carbon, glassy carbon, etc., or combinations thereof. The conductive material may also include any conductive carbon material described with respect to the cathode material, including but not limited to acetylene black, single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, graphyne, or any combination thereof.

[0066] The anode material 5 may also include a binder. Typically, the binder serves to hold the particles of the electroactive material (such as Zn used in the anode, etc.) together and in contact with the current collector. The binder may be present in a concentration of 0 wt% to 10 wt.%. The binder may include a water-soluble cellulose-based hydrogel such as methyl cellulose (MC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPH), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl methyl cellulose (HEMC), carboxymethyl hydroxyethyl cellulose and hydroxyethyl cellulose (HEC), which act as thickeners and strong binders and have been cross-linked with good mechanical strength and conductive polymers such as polyvinyl alcohol, polyvinyl acetate, polyaniline, polyvinyl pyrrolidone, polyvinylidene fluoride and polypyrrole. The binder may also be a cellulose film sold in the form of cellophane. The binder may also be This is a very resistive material, but is widely used in industry due to its good rollability. In some embodiments, the binder may be present in the anode material in an amount of about 2 wt.% to about 10 wt.%, or about 2 wt.% to about 7 wt.%, or about 4 wt.% to about 6 wt.%, based on the total weight of the anode material.

[0067] In some embodiments, the anode material 5 can be used alone without a separate anode current collector 4, although a tab or other electrical connection can still be provided to the anode material 5. In this embodiment, the anode material can have the form or structure of a foil, mesh, perforated layer, foam, felt, or powder.

[0068] 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 all of those described with respect to the cathode 12. The anode material 5 may be pressed onto the anode current collector 4 to form the anode 13. For example, the pressure may be between 1000 psi and 20,000 psi (6.9×10 6 and 1.4×10 8 The anode material 5 is adhered to the anode current collector 4 by pressing under a pressure of 1000 psi (about 1000 psi). The anode material 5 may be adhered to the anode current collector 4 in the form of a paste. When a tab of the anode current collector 4 is present, it may extend outside the device to form a current collector tab.

[0069] High voltage batteries can be achieved by polymerizing the anode electrolyte, which makes it possible to remove relatively expensive separators (e.g., ion selective membranes) used to make dual electrolyte batteries work in liquid electrolyte systems. In some embodiments, the anode electrolyte can be an alkaline electrolyte, while the cathode electrolyte can be an acidic or neutral solution. The alkaline electrolyte in the anode electrolyte can be a hydroxide, such as potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, cesium hydroxide, or any combination thereof. The resulting anode electrolyte can have a pH greater than 7. In some embodiments, the pH of the anode electrolyte can be greater than or equal to 10 and less than or equal to about 15.13.

[0070] In addition to hydroxide, the anode electrolyte may include additional components. In some embodiments, the alkaline electrolyte may have zinc oxide, potassium carbonate, potassium iodide and potassium fluoride as additives. When the zinc compound is present in the anode electrolyte, the anode electrolyte may include 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 perchlorate, lithium oxalate, lithium fluoride, lithium carbonate, lithium bromate, acrylic acid, N,N'-methylenebisacrylamide, potassium persulfate, ammonium persulfate, sodium persulfate, or a combination thereof.

[0071] As described herein, the anolyte can be polymerized or gelled. The resulting anolyte can be semi-solid and unable to flow in the battery. This can be used to limit or prevent any mixing between the anolyte and the cathode electrolyte. Any suitable technique can be used to polymerize the anolyte. Although a variety of polymerization methods can be used, in some embodiments, a mixture of acrylic acid, N,N'-methylenebisacrylamide and an alkaline solution can be prepared at a temperature of about 0°C. Any additives can then be added to the solution. For example, when zinc oxide is used in the anolyte, it can be dissolved in an alkaline solution after mixing the precursor components, where the zinc oxide is beneficial during the electrochemical cycle of the anode. In order to polymerize the resulting mixture, an initiator (such as potassium persulfate) can be added to initiate the polymerization process and form a solid polyelectrolyte. The resulting polymerized anolyte is stable, and its interface can prevent the mixing of the cathode electrolyte and the anolyte from generating a high voltage source.

[0072] The polymerization process can occur before or after the battery 10 is constructed. In some embodiments, the anolyte can be polymerized and placed in a tray to form a sheet. Once polymerized, the sheet can be cut into a suitable size and shape, and one or more layers can be used to form the anolyte in contact with the anode 13. In some embodiments, before the anolyte 6 is fully polymerized, the anolyte can be formed into a polymerization mixture together with an initiator and placed in the battery 10. The anolyte 6 can then be polymerized in situ within the battery 10.

[0073] like Figure 1 As shown, the cell 10 may not include a separator. The ability to form the cell 10 without a separator enables the overall cost of the cell to be reduced while having the same or similar performance as a cell with a separator.

[0074] In some embodiments, a separator may be provided between the anode 13 and the cathode 12 when the electrodes are constructed into a battery. Figure 3 An embodiment of a cell 20 is shown that is similar to cell 10, except that cell 20 may have a separator 9 disposed between cathode electrolyte 3 and anode electrolyte 6. The remainder of cell 20 may be the same as described with respect to Figure 1 The battery 10 is the same as described above. In this embodiment, the separator 9 may include one or more layers. Suitable layers may include, but are not limited to, polymer separator layers, such as sintered polymer films, polyolefin films, polyolefin nonwoven films, cellulose films, cellophane, battery-grade cellophane, hydrophilically modified polyolefin films, or combinations thereof. As used herein, the phrase "hydrophilically modified" refers to a material having 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°. Polyolefins can be modified by, for example, adding TRITON X-100TM Or modified by oxygen plasma treatment. In some embodiments, the spacer 9 may include In one embodiment, the separator 9 may include a FS2192SG membrane, which may be a polyolefin nonwoven membrane available from Freudenberg, Germany. In some embodiments, the separator may include a lithium superion conductor. Sodium superionic conductor (NASION), Bipolar membrane, water electrolysis membrane, composite of polyvinyl alcohol and graphene oxide, polyvinyl alcohol, cross-linked polyvinyl alcohol, or a combination thereof.

[0075] While the separator 9 may comprise a variety of materials, the use of a polymerized or gelled anode electrolyte 6 may allow for the use of a relatively inexpensive separator 9. For example, the separator 9 may comprise Polyvinyl alcohol, Composites of polyvinyl alcohol and graphene oxide, cross-linked polyvinyl alcohol, A carbon-polyvinyl alcohol composite is placed between the two electrolytes. Using a separator 9 between the two electrolytes can help improve the cycle life of the battery 20, but is not necessary in all embodiments.

[0076] In some embodiments, both the cathode electrolyte and the anode electrolyte may be polymerized or gelled. Figure 4 As shown, the battery 40 may include a polymerized or gelled cathode electrolyte 11 and a polymerized or gelled anode electrolyte 6, with no separator provided between the cathode electrolyte 11 and the anode electrolyte 6. The rest of the battery 40 may be connected to the Figure 1 The present invention is the same as or similar to those described with respect to the battery 10 in , and for the sake of brevity, similar parts are not described repeatedly.

[0077] In cell 40, cathode electrolyte 11 may include the same or similar components as those described for cathode electrolyte 3, including an acidic or neutral electrolyte, and one or more optional additives. The resulting cathode electrolyte may then polymerize to form a gelled electrolyte that resists migration and mixing with anode electrolyte 6. Catholyte 11 may be polymerized using any suitable polymerization technique for use in acidic or neutral solutions.

[0078] In some embodiments, the cathode electrolyte 11 can be polymerized to produce a hydrogel by mixing an acidic or neutral solution with polyvinyl alcohol (PVA). This gelled structure can be further processed with two to three thawing cycles, wherein the acidic-PVA hydrogel structure can be cooled to a temperature of -20°C to 0°C and then raised back to room temperature and repeated. In order to improve the performance of the acidic hydrogel, quinone-based compounds such as hydroquinone and Alizarin Red S can be added to the mixture of polyvinyl alcohol, acidic or neutral solution before the thawing step. Any other suitable polymerization or gelation technique or process can also be used. Once gelled, the cathode electrolyte 11 and the anode electrolyte 6 can be placed in contact within the housing 7 and used within the battery 40.

[0079] Figure 5 Another embodiment of a battery 50 is shown, in which the polymerized or gelled cathode electrolyte 11 and the polymerized or gelled anode electrolyte 6 may be separated by a separator 9. The rest of the battery 50 may be similar to that described with respect to FIG. Figure 1 Battery 10 and about Figure 4 The parts of the battery 40 described in FIG. 1 are the same or similar, and for the sake of brevity, similar parts are not described repeatedly. Figure 5 As shown, a separator 9 may be placed between the gelled cathode electrolyte 11 and the gelled anode electrolyte 6. The separator 9 may include a Figure 3 The use of separator 9 in battery 50 can be used to improve the cycle life of battery 50.

[0080] In addition to the above embodiments, the battery can be a fully solid-state high voltage battery (SS-HiVAB). In some embodiments, the SS-HiVAB can deliver energy at a higher voltage than any comparable battery currently available on the market. In these embodiments, the cathode can include manganese dioxide (MnO2) or lead oxide (PbO2), and the anode can include zinc (Zn), aluminum (Al), magnesium (Mg) and / or iron (Fe). The high voltage can be achieved by maintaining different pH in the cathode and anode compartments of the battery, where the cathode is typically in an acidic to neutral solution and the anode is in an alkaline / basic solution. The fully solid-state aspect can be achieved by polymerizing the electrolytes of the cathode and anode (e.g., the cathode electrolyte and the anode electrolyte). An increase in ionic conductivity in the system can be achieved by adding ammonium salts to the cathode electrolyte and / or potassium salts to the anode electrolyte. Better voltage characteristics can also be achieved by using additional dopants in the cathode electrode and / or the electrolyte. The resulting configuration can realize all-solid-state MnO2|Zn, MnO2|Al, MnO2|Mg and MnO2|Fe and PbO2|Zn, PbO2|Al, PbO2|Mg and PbO2|Fe high-voltage aqueous batteries (HiVABs) with potentials between 2.5 and 34 V for the MnO2|Zn system and ~3 V for the PbO2|Zn system. The manganese dioxide disclosed in this patent application can achieve 80% to 100% of its one-electron (308 mAh / g) and two-electron (617 mAh / g) capacity, respectively. Other forms of manganese oxides, such as spinel manganese oxides (Mn3O4, LiMn2O4, ZnMn2O4) and manganese oxide (MnO) can also be used as cathodes.

[0081] Based on the theoretical capacities of MnO2 and Zn, the disclosed SS-HiVAB can provide a battery with very high energy density. MnO2 reacts with the acidic electrolyte with two electrons, delivering 617 mAh / g. However, it can also cycle one electron at 308 mAh / g. These two capacity values ​​of MnO2 make it a very energy-dense cathode. Compared to conventional lithium-ion cathodes, which typically cycle at capacities of 140 mAh / g to 180 mAh / g, the MnO2 in the new SS-HiVAB cycles at approximately 2-3.5 times more. Furthermore, the carbon anode in a Li-ion battery has a theoretical capacity of only 375 mAh / g, while the zinc in the new SS-HiVAB has a theoretical capacity of 820 mAh / g based on the 2e reaction. The high capacity of the cathode and anode, combined with the high voltage of 2.45-4 V, makes these SS-HiVABMnO2|Zn cathodes much higher in energy density than lithium-ion batteries.

[0082] The battery may include Figures 1 to 5Specifically, the battery may include: a cathode material containing manganese dioxide (MnO2) or lead oxide (PbO2). The cathode material may also include Figures 1 to 5 For example, MnO2 can exist in various polymorphic forms, such as α, δ, γ, β, λ, ε, and electrolytic manganese dioxide, all of which are described herein.

[0083] When the cathode material contains MnO2, the resulting battery can cycle at 100% of 308 mAh / g and 50% to 100% of 617 mAh / g. This can be achieved in acidic electrolytes because Mn ions dissolve. 4+ state, and is reduced to Mn when fully discharged to 617 mAh / g. 2+ In alkaline electrolyte, it is difficult to fully cycle the two-electron capacity of 617 mAh / g due to the insolubility of Mn ions.

[0084] The cathode may include a cathode current collector and may be used as described herein. Figures 1 to 5 any of the materials, forms and techniques described.

[0085] about Figures 1 to 5Any of the catholyte compositions and additives described may also be used with the catholyte in SS-HiVAB.The catholyte may be polymerized or gelled using any of the techniques described herein. For example, the cathode electrolyte can include potassium permanganate, sodium permanganate, lithium permanganate, calcium permanganate, manganese sulfate, manganese chloride, manganese nitrate, manganese perchlorate, manganese acetate, manganese bis(trifluoromethanesulfonate), manganese trifluoromethanesulfonate, manganese carbonate, manganese oxalate, manganese fluorosilicate, manganese ferrocyanide, manganese bromide, magnesium sulfate, ammonium chloride, ammonium sulfate, ammonium hydroxide, zinc sulfate, zinc trifluoromethanesulfonate, zinc acetate, zinc nitrate, bismuth chloride, bismuth nitrate, nitric acid, sulfuric acid, hydrochloric acid, sodium sulfate, potassium sulfate, 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, carboxymethyl cellulose, xanthan gum, carrageenan, acrylamide, potassium persulfate, sodium persulfate, ammonium persulfate, N,N'-methylenebisacrylamide, or a combination thereof. In some embodiments, the cathode electrolyte solution may include manganese sulfate, ammonium chloride, ammonium sulfate, manganese acetate, potassium permanganate, and / or a salt of permanganate, wherein the concentration of the additive may be between 0 M and 10 M. Depending on the type of manganese salt used, the voltage of the battery system may be different. For example, in a manganese sulfate electrolyte, the voltage of SS-HiVAB is about 2.45-2.5 V, while in a potassium permanganate electrolyte, the voltage of SS-HiVAB is about 2.8-2.9 V.

[0086] Acids may be added to these electrolytes to increase the solubility of Mn ions, improve the ionic conductivity of the electrolyte, and adjust the pH to a desired value. The SS-HiVAB gelled cathode electrolyte may comprise sulfuric acid, hydrochloric acid, and / or nitric acid, and the acid may be present in the cathode electrolyte at a concentration between 0 and 16 M. In some embodiments, the polymerized cathode electrolyte solution may comprise potassium permanganate or a salt of a permanganate and an acid, and the molar ratio of potassium permanganate or a salt of a permanganate to the acid may be between 5:1 and 1:5 or between 5:1 and 1:5.

[0087] In some embodiments, the SS-HiVAB may include one or more additives, which include ammonium ions in the cathode electrolyte. When the cathode electrolyte is gelled, the ionic conductivity of the cathode electrolyte decreases. In order to improve the ionic conductivity of the system in the gelled state, ammonium salts such as ammonium chloride, ammonium acetate, and ammonium hydroxide can be added to the cathode electrolyte. In some embodiments, ammonium chloride can be used as an additive because it can reduce the overpotential of MnO2 during discharge and charge, and can help promote faster reaction kinetics, especially in solid gels. In some embodiments, the SS-HiVAB cathode electrolyte may include a permanganate as described herein for the cathode electrolyte.

[0088] The SS-HiVAB cathode electrolyte can have a pH greater than or equal to 0 and less than or equal to 7. The cathode electrolyte is stable over a temperature range of 0°C to 200°C.

[0089] The anode of SS-HiVAB can be used with Figures 1 to 5 The anode of the SS-HiVAB may be the same or similar to the anode described in . The anode of the SS-HiVAB may include an electroactive material including zinc (Zn), aluminum (Al), magnesium (Mg) and / or iron (Fe). The anode may also include Figures 1 to 5 All additives and components described for the battery described herein. The anode may include an anode current collector and may be used Figures 1 to 5 can be formed by any of the materials, forms and techniques described.

[0090] The anolyte may be a gelled alkaline electrolyte comprising Figures 1 to 5 Any polymeric or gelled anolyte described herein. A higher concentration of alkaline electrolyte is generally used to increase the solubility of the metal in the gel state. For example, the higher concentration of the anolyte may be between 25 wt.% and 70 wt.%. The alkaline electrolyte may comprise any alkaline electrolyte described herein, including potassium hydroxide, sodium hydroxide, lithium hydroxide, barium hydroxide, calcium hydroxide, etc. Other salts and additives may also be added to the alkaline electrolyte, including Figures 1 to 5Those described. For example, additional components used in the anode electrolyte may include 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, zinc trifluoromethanesulfonate, aluminum sulfate, ferric sulfate, aluminum chloride, ferric chloride, magnesium chloride, magnesium sulfate, magnesium perchlorate, aluminum perchlorate, aluminum trifluoromethanesulfonate, ferric trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, 1-methyl-1-propylpyrrolidinium chloride, 1-ethyl-3-methylimidazolium chloride, 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 perchlorate, lithium oxalate, lithium fluoride, lithium carbonate, lithium bromate, acrylic acid, N,N'-methylenebisacrylamide, potassium persulfate, ammonium persulfate, sodium persulfate, or combinations thereof. The gelled anode electrolyte may have a pH between about 7 and 15.13.

[0091] SS-HiVAB can be used with Figures 1 to 5 In some embodiments, no spacer is required. Then, the SS-HiVAB can be used as Figure 4 The configuration shown has a gelled cathode electrolyte 11 and a gelled anode electrolyte 6, with no separator between the cathode electrolyte 11 and the anode electrolyte 6. These two gelled electrolytes can withstand long-term cycling without degradation. If a separator is used, an inexpensive separator such as cellophane, polyvinyl alcohol, or cross-linked polyvinyl alcohol can be used.

[0092] about Figures 1 to 5 The anolyte in the battery described herein describes any polymerization and / or gelation process. Although a method for polymerizing or gelling the cathode electrolyte and the anolyte is described, other methods known in the art can be used to prepare the gelled cathode electrolyte and / or anolyte. In the spirit of the present disclosure, the use of two gelling systems is a feature that enables the battery to operate at high voltage and high capacity, regardless of the method used to gel the electrolyte.

[0093] Manganese dioxide can be cycled in an acidic electrolyte at close to its theoretical one- and two-electron capacities because the electrolyte allows the manganese ions to completely dissolve during discharge and re-electrode as manganese dioxide during recharge. Without the use of expensive ion-selective or bipolar membranes, the system is very inexpensive, making it suitable for a wide range of applications where cost is the primary limiting factor in the use of rechargeable energy storage systems.

[0094] The resulting battery can have an open circuit potential between 2 and 3.6 V. The battery can be used as a primary battery or a secondary battery, allowing the battery to be cycled (eg, discharged and charged) multiple times.

[0095] The system is also relatively inexpensive compared to more expensive systems such as lithium-ion systems and can achieve primary system cost targets in the range of typically <$15 / kWh, but has the added advantage of being rechargeable, making the battery's lifetime cost the lowest of all available chemistries on the market. The system also has an energy efficiency of >80% to 90% depending on the cycle rate used, making the cost to the consumer very viable over the life of the battery.

[0096] Example

[0097] Having described the embodiment as a whole, the following examples are given in the form of specific embodiments of the present application and confirm the practice and advantages of the present application. It should be understood that these examples are given by way of illustration and are not intended to limit the specification or claims in any way.

[0098] Example 1

[0099] The cathode solution is prepared by mixing 1M manganese sulfate monohydrate with 0.5M sulfuric acid. Typically, the ratio between the two solutions is maintained at 2, but this can vary depending on the conditions of battery operation. The anode solution is prepared by mixing potassium particles with deionized water to produce a 45 wt.% potassium hydroxide solution. Polymerization of the anode solution is accomplished by first dissolving 100 mg of N,N'-methylenebisacrylamide (MBA) in 20 mL of acrylic acid (AA). At the same time, the 45 wt.% potassium hydroxide (KOH) solution is cooled to below 0°C. The mixture of MBA and AA is then slowly added to the cold 45 wt.% KOH solution until it forms a uniform solution. The solution is added slowly due to the heat generated when AA and KOH are mixed. To polymerize the mixed solution, an initiator is added. The initiator used in this example is potassium persulfate (4 wt.% solution). After adding the initiator to the mixed solution, the electrolyte will polymerize / gel within a few seconds. To slow down the polymerization reaction, the mixed solution can be kept cool. This polymerized electrolyte can be cut into sheets of any size or shape. In this example, a solution containing an initiator is added to the cell chamber containing a zinc (Zn) anode to polymerize within the cell itself.

[0100] The anode used in this cell is a zinc anode. The zinc anode can be a powder electrode, foil, or mesh and can be doped or coated with bismuth, bismuth oxide, indium, and indium hydroxide, if applicable. The cathode used in this cell is electrolytic manganese dioxide (MnO2) mixed with carbon nanotubes (CNTs). The electrode mixture consists of 85 wt.% MnO2 and 15 wt.% CNTs. This mixture is coated on carbon felt and dried at 60°C.

[0101] The battery assembly uses the cathode and anode described above and immerses them in their respective cathode and anode electrolytes. The battery was designed to be cycled at 20% of its single electron capacity (308 mAh / g) at C / 2 (where C-rate is a measure of the rate at which a battery is charged or discharged relative to its capacity). The cycling results for this battery are shown in Figure 2. Figure 6 As shown, it can be seen that the open circuit potential is 2.47V. Figure 6 In the study, the battery was shown to cycle very stably between 2.67 V and 2.2 V. This is the first time in the literature that an aqueous MnO2-Zn battery has been shown to cycle above 2 V. Figure 7 The capacity provided over the entire life cycle was shown to be successfully released at 60 mAh / g and charged to its designed capacity. In this new system, the cycle was also very stable. The energy efficiency of the battery was as high as ~85% to 87% ( Figure 8 ), which is important for any energy storage system. This is the first demonstration of an MnO2-Zn battery exceeding 2V.

[0102] Example 2

[0103] In this example, the design of the cell was the same as described in Example 1. The difference in this example was that the cell was cycled at C / 5 and C / 10 at 100% single electrons (308 mAh / g). The cycling results are shown in Figure 2. Figure 9 As shown in Figure 2, the battery can be cycled very stably at high C-rates, reaching its theoretical single-electron capacity. When the C-rate is changed to C / 10, the cycling and energy efficiency of the battery become quite good.

[0104] Example 3

[0105] In this example, the design of the cell was exactly the same as described in Example 1. The difference in this example was that the cell was cycled at a high capacity (Ah), at 100% single electrons (308 mAh / g) at C / 40. This was done to demonstrate the use of this new cell in a primary application. The primary battery industry is looking for inexpensive high voltage battery chemistries. Unfortunately, alkaline and Leclanch chemistries have relatively low voltages of approximately 1.1-1.2 V and cannot compete with Li-ion in terms of voltage. The first discharge of this new cell was as follows: Figure 10 As shown, complete single-electron capacity transfer is seen between 2.1 and 2.3 V. This is a breakthrough in aqueous battery systems.

[0106] Example 4

[0107] The cathode solution is prepared by mixing 0.5M potassium permanganate with 0.5M sulfuric acid. Typically, the ratio between the two solutions is maintained at 1:3, but it can vary depending on the conditions of battery operation. The anode solution is prepared by mixing potassium particles with deionized water to produce a 45wt.% solution. Polymerization of the anode solution is accomplished by first dissolving 100mg of N,N'-methylenebisacrylamide (MBA) in 20mL of acrylic acid (AA). At the same time, the 45wt.% potassium hydroxide (KOH) solution is cooled to below 0°C. The mixture of MBA and AA is then slowly added to the 45% cold KOH solution until it forms a uniform solution. The solution is added slowly due to the heat generated when AA is mixed with KOH. In order to polymerize the mixed solution, an initiator is used. The initiator used in this example is potassium persulfate (4wt.% solution). After adding the initiator to the mixed solution, the electrolyte can polymerize / gel within a few seconds. To slow down the polymerization reaction, the mixed solution can be kept cool. This polyelectrolyte can be cut into sheets of any size or shape. In this example, a solution containing an initiator is added to the cell chamber containing a zinc (Zn) anode to polymerize within the cell itself.

[0108] The anode used in this battery is a zinc anode. The Zn anode can be a powder electrode, foil, or mesh and can be doped or coated with bismuth, bismuth oxide, indium, and indium hydroxide, if necessary. The cathode used in this battery is electrolytic manganese dioxide (MnO2) mixed with carbon nanotubes (CNTs). The electrode mixture consists of 85 wt.% MnO2 and 15 wt.% CNTs. This mixture is coated on carbon felt and dried at 60°C.

[0109] The battery assembly uses the cathode and anode described above and immerses them in their respective cathode and anode electrolytes. The battery is designed to be cycled at C / 2 at 20% of the single electron capacity (308 mAh / g). The cycling results of the battery are shown in Figure 2. Figure 11 As shown, it can be seen that the open circuit potential is 2.8V. Figure 11 In the figure, the open circuit potential of MnO2|Zn batteries with different electrolytes is shown. If manganese sulfate is used as the cathode electrolyte, the open circuit potential is usually between 2.4-2.5 V, however, permanganate can increase the potential to 2.8 V. The traditional alkaline battery using 45 wt.% KOH shows an open circuit potential of ~1.55 V, which is much lower than the newly designed battery. Figure 12 In Figure 2, the first three discharge curves of three cells containing different electrolytes are shown. It can be seen that using permanganate as the electrolyte on the cathode brings an energy gain of ~1.4 V compared to a conventional alkaline cell. Figure 13The cycle life of the new battery is shown, where it can be seen that it is rechargeable. This is the first time in the literature that an aqueous MnO2-Zn battery cycling to ~2.8V has been reported.

[0110] Example 5

[0111] In this example, the design of the cell was exactly the same as described in Example 4. The difference in this example was that the cell was cycled at C / 10 at 100% single electrons (308 mAh / g). The cycling results are shown in Figure 4. Figure 14 As shown, the battery is able to deliver its full theoretical first electron capacity at just 2.62V, a breakthrough for battery systems. This is the first reported high-voltage MnO2|Zn battery with a capacity of 308 mAh / g above 2.6V. This opens up the use of aqueous batteries in applications currently dominated by expensive and hazardous lithium-ion batteries.

[0112] Example 6

[0113] In this example, the design of the cell is exactly the same as that described in Example 4. The difference in this example is that the cell is continuously cycled at C / 20 at 100% single electron (308 mAh / g). The cycling results are shown in Figure 4. Figure 15 The battery was able to achieve full 1e (308 mAh / g). Another battery was cycled multiple times under the same conditions and then stopped charging. Figure 16 An SEM image of such a charged cathode is shown, in which the birnessite structure is visible. XRD at the end of charge also shows γ-MnO2, indicating the formation of manganese dioxide, as shown in Figure 17 As shown. Figure 18 The patented battery design is shown in Figure 1 relative to previous battery literature. This is the first demonstration of an aqueous manganese dioxide|zinc battery breaking the 2V barrier, making it highly competitive with lithium-ion batteries in terms of energy density and cost. This represents a significant advancement in aqueous battery chemistry.

[0114] Example 7

[0115] The method for preparing a solid gelled cathode electrolyte involves adding acrylamide to a mixture of 1M manganese sulfate and 0.5M H2SO4 solution, or to a mixture of 1M manganese sulfate, 3M ammonium sulfate and 0.5M H2SO4 solution, or to a mixture of 0.5M potassium permanganate and 0.5M sulfuric acid solution. If 200mL of total solution is prepared, ~50g of acrylamide is added to the solution and mixed vigorously at 70°C to 90°C for at least 1 hour until the solution is homogeneous. After the solution is thoroughly mixed, 100mg to 700mg of N,N'-methylenebisacrylamide and 100mg to 1500mg of potassium persulfate are added to the solution and mixed for 2 to 48 hours until the solution is completely gelled. The gelled solution is shown in Figure 1. Figure 19 shown.

[0116] Similarly, a solid gelled anodic electrolyte was prepared by mixing potassium particles with deionized water to produce a 45 wt.% solution. The polymerization of the anodic solution was accomplished by first dissolving 100 mg of N,N'-methylenebisacrylamide (MBA) in 20 mL of acrylic acid (AA). At the same time, the 45 wt.% potassium hydroxide (KOH) solution was cooled to below 0°C. The mixture of MBA and AA was then slowly added to the cold 45 wt.% KOH solution until a uniform solution was formed. Since AA generates heat when mixed with KOH, the solution was added slowly. In order to polymerize the mixed solution, an initiator was used. The initiator used in this example was potassium persulfate (4 wt.% solution). After the initiator was added to the mixed solution, the electrolyte polymerized / gelled within a few seconds. To slow down the polymerization reaction, the mixed solution can be kept at a low temperature. This polymerized electrolyte can be cut into sheets of any size or shape as needed. A diagram of a zinc mesh embedded in a gelled 45 wt.% potassium hydroxide solution is shown in FIG. Figure 19 In the lower left photo.

[0117] Example 8

[0118] Ammonium chloride was added to a solution of 1 M manganese sulfate and 0.5 M sulfuric acid to help improve ionic conductivity and produce a better overall potential. This was demonstrated in cells with a liquid cathode electrolyte before polymerization. Three cells were made with a liquid cathode electrolyte and a gelled 45 wt.% KOH anolyte. Zinc mesh was used as the anode. The cathode was 85 wt.% manganese dioxide and 15 wt.% carbon nanotubes bonded to carbon felt. The mass loading of the cathode was ~10-20 mg / cm 2These cells were fabricated with a cellophane separator between the liquid cathode electrolyte and the gelled anode electrolyte. A control cell was made with 1M manganese sulfate and 0.5M sulfuric acid as the cathode electrolyte; another cell had a cathode electrolyte of 1M manganese sulfate and 0.5M sulfuric acid with 3M ammonium chloride added and a 1M manganese acetate electrolyte to test whether acetate ions contribute to the potential and ionic conductivity. The open circuit potentials of the three cells are shown in Figure 2. Figure 20 It is obvious that after 7 hours of open circuit, the battery with a cathode electrolyte of 1M manganese sulfate and 0.5M sulfuric acid with 3M ammonium chloride added and an anode electrolyte of 45 wt.% gelled potassium hydroxide showed a maximum potential of 2.58V. The discharge curves of these batteries are also shown in Figure 21 In the study, the cell with manganese sulfate as the cathode electrolyte was designed to achieve a theoretical capacity of 308 mAh / g of MnO2, while the cell with acetate as the cathode electrolyte was designed to achieve 20% of 308 mAh / g. All cells were discharged to their designed capacity, but the cell with 1 M manganese sulfate and 0.5 M sulfuric acid with 3 M ammonium chloride added to the cathode electrolyte gave the best potential for achieving capacity, which translates to the highest energy achieved. Therefore, the addition of 3 M ammonium chloride contributes to higher energy attainment due to its better potential and capacity accessibility. Figure 22 As shown, the cycling performance of the cell with a catholyte of 1 M manganese sulfate and 0.5 M sulfuric acid with the addition of 3 M ammonium chloride showed 100% recharge to its theoretical capacity of 308 mAh / g.

[0119] Example 9

[0120] To fabricate a fully solid-state battery, a cathode electrolyte of 1 M manganese sulfate and 0.5 M sulfuric acid supplemented with 3 M ammonium chloride was fully gelled according to the protocol mentioned in Example 7. This gelled polymeric cathode electrolyte was placed on top of a cathode that was carbon felt with a loading of ∼10 mg / cm 2 Up to 20 mg / cm 2 The anode was 45 wt.% gelled KOH with a zinc mesh. Two types of cells were fabricated. One cell combined two solid electrolytes and their respective electrodes without a membrane, and the other had a cellophane separator between the two electrolytes. The open circuit potentials of the two cells were as follows: Figure 23 As shown. After being kept open circuit for 7 hours, the potential of both batteries remained very stable. This is of broad breakthrough significance because it demonstrates for the first time the creation of a membraneless fully solid-state high-voltage aqueous MnO2|Zn battery (SS-HiVAB). The absence of separators helps to reduce the overall cost of the battery. The discharge performance of the two batteries was also tested. Both are designed to discharge ~120mAh / g, with performance as shown Figure 24There is no difference in performance between the membraneless battery and the cellophane separator battery. The cycling performance of the membraneless high voltage solid-state MnO2|Zn battery is also shown in Figure 25 The breakthrough battery is capable of reversible cycling at its designed capacity without any capacity or energy decay. This is the first report of a fully solid-state, high-voltage, membraneless MnO2|Zn aqueous battery that breaks the 2.5V barrier.

[0121] Various systems and methods have been described herein, some implementations of which may include, but are not limited to:

[0122] In a first embodiment, a high voltage aqueous battery comprises: a cathode comprising a cathode electroactive material; an anode comprising an anode electroactive material; a cathode electrolyte solution in contact with the cathode, wherein the cathode electrolyte is not in contact with the anode; and a polymerized anode electrolyte solution in contact with the anode.

[0123] A second embodiment may include the battery of the first embodiment, wherein the cathode electroactive material includes manganese dioxide.

[0124] A third embodiment may include the cell of the second embodiment, wherein the anode electroactive material includes zinc, aluminum, or a combination thereof.

[0125] A fourth embodiment may include the battery of any of the first through third embodiments, wherein the cathode electroactive material comprises manganese dioxide or lead oxide.

[0126] A fifth embodiment may include the battery of any of the first to fourth embodiments, wherein the anode electroactive material includes zinc (Zn), aluminum (Al), magnesium (Mg), iron (Fe), or combinations thereof.

[0127] A sixth embodiment may include the battery of any of the first to fifth embodiments, wherein the anode includes iron oxide, iron hydroxide, bismuth oxide, bismuth, indium oxide, indium hydroxide, indium, copper, copper oxide, copper hydroxide, manganese oxide, or any combination thereof.

[0128] A seventh embodiment may include the battery of any of the first to sixth embodiments, wherein the cathode and anode each comprise a current collector made of carbon, lead, copper, nickel, silver, bismuth, titanium, magnesium, aluminum, gold, or combinations thereof.

[0129] An eighth embodiment may include the battery of the seventh embodiment, wherein the current collector is a mesh, foil, foam, felt, fiber, porous monolith, or a combination thereof.

[0130] A ninth embodiment may include the cell of any one of the first to eighth embodiments, wherein the cathode electrolyte solution comprises potassium permanganate, sodium permanganate, lithium permanganate, manganese sulfate, manganese chloride, manganese nitrate, manganese perchlorate, manganese acetate, manganese bis(trifluoromethanesulfonate), manganese trifluoromethanesulfonate, manganese carbonate, manganese oxalate, manganese fluorosilicate, manganese ferrocyanide, manganese bromide, magnesium sulfate, zinc sulfate, zinc trifluoromethanesulfonate, zinc acetate, zinc nitrate, bismuth chloride, bismuth nitrate, nitric acid, sulfuric acid, hydrochloric acid, sodium sulfate, potassium 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, or a combination thereof.

[0131] A tenth embodiment may include the cell of any one of the first to ninth embodiments, wherein the catholyte solution has a pH between -1.2 and 7.

[0132] An eleventh embodiment may include the cell of any one of the first to tenth embodiments, wherein the cathode electrolyte solution comprises sulfuric acid, hydrochloric acid, or nitric acid at a concentration greater than 0 and less than or equal to 16M.

[0133] A twelfth embodiment may include the cell of any one of the first to eleventh embodiments, wherein the catholyte solution comprises potassium permanganate or a salt of a permanganate at a concentration greater than 0 and less than or equal to 5M.

[0134] A thirteenth embodiment may include the cell of any one of the first through twelfth embodiments, wherein the catholyte solution comprises potassium permanganate or a salt of permanganate and an acid, wherein the molar ratio of potassium permanganate or a salt of permanganate to acid is 1:3.

[0135] A fourteenth embodiment may include the battery of any of the first through thirteenth embodiments, wherein the cathode electroactive material comprises manganese dioxide mixed with carbon.

[0136] A fifteenth embodiment may include the battery of the fourteenth embodiment, wherein the carbon is graphite, carbon fiber, carbon black, acetylene black, single-walled carbon nanotubes, multi-walled carbon nanotubes, nickel- or copper-coated carbon nanotubes, a dispersion of single-walled carbon nanotubes, a dispersion of multi-walled carbon nanotubes, graphene, graphyne, graphene oxide, or a combination thereof.

[0137] A sixteenth embodiment may include the battery of any one of the first to fifteenth embodiments, wherein the polymeric anolyte solution comprises 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 perchlorate, lithium oxalate, lithium fluoride, lithium carbonate, lithium bromate, acrylic acid, N,N'-methylenebisacrylamide, potassium persulfate, ammonium persulfate, sodium persulfate, or a combination thereof.

[0138] A seventeenth embodiment may include the cell of any of the first through sixteenth embodiments, wherein the polymeric anolyte solution has a pH between 10 and 15.13.

[0139] An eighteenth embodiment may include the battery of any one of the first to seventeenth embodiments, wherein the anode is a foil structure, a mesh structure, a perforated structure, a foam structure, a felt structure, or a powder structure.

[0140] A nineteenth embodiment may include the battery of any one of the first to eighteenth embodiments, further comprising: a separator disposed between the cathode electrolyte solution and the polymerized anode electrolyte solution.

[0141] A twentieth embodiment may include the battery of the nineteenth embodiment, wherein the separator is polyvinyl alcohol, a composite of polyvinyl alcohol and graphene oxide, or a combination thereof.

[0142] A twenty-first embodiment may include the battery of any one of the first through twentieth embodiments, wherein the catholyte solution is polymeric.

[0143] A twenty-second embodiment may include the battery of any one of the first to twenty-first embodiments, wherein the battery has an open circuit potential between 2V and 4V.

[0144] In a twenty-third embodiment, a high voltage aqueous battery comprises: a cathode comprising manganese dioxide, spinel manganese oxide (Mn3O4) or manganese oxide (MnO); an anode comprising zinc, aluminum, magnesium or iron; a polymerized cathode electrolyte solution in contact with the cathode; and a polymerized anode electrolyte solution in contact with the anode.

[0145] A twenty-second embodiment may include the cell of the twenty-third embodiment, wherein the polymeric catholyte solution comprises a salt of manganese sulfate, ammonium chloride, ammonium sulfate, manganese acetate, potassium permanganate, or permanganate at a concentration between 0 and 10 M.

[0146] A twenty-fifth embodiment may include the cell of the twenty-third or twenty-fourth embodiment, wherein the polymeric catholyte solution comprises sulfuric acid, hydrochloric acid, or nitric acid at a concentration between 0 and 16 M.

[0147] A twenty-sixth embodiment may include the cell of any of embodiments twenty-third through twenty-fifth, wherein the polymeric catholyte solution comprises potassium permanganate or a salt of a permanganate and an acid, wherein the volume ratio of potassium permanganate or a salt of a permanganate to the acid is from 5:1 to 1:5.

[0148] A twenty-seventh embodiment may include the cell of any of embodiments twenty-third through twenty-sixth, wherein the polymeric catholyte solution comprises manganese sulfate, ammonium chloride, and an acid, wherein the volume ratio of the mixture of manganese sulfate and ammonium chloride to the acid is from 5:1 to 1:5.

[0149] A twenty-eighth embodiment may include the battery of any one of the twenty-third to twenty-seventh embodiments, wherein the manganese dioxide is mixed with carbon.

[0150] A twenty-ninth embodiment may include the battery of the twenty-eighth embodiment, wherein the mixture of manganese dioxide and carbon further includes cobalt oxide, cobalt hydroxide, lead oxide, lead hydroxide, or a combination thereof.

[0151] In a thirtieth embodiment, a high voltage aqueous battery comprises: a cathode comprising lead oxide (PbO2); an anode comprising zinc, aluminum, magnesium or iron; a polymerized cathode electrolyte solution in contact with the cathode; and a polymerized anode electrolyte solution in contact with the anode.

[0152] A thirty-first embodiment may include the cell of the thirtieth embodiment, wherein the polymeric catholyte solution comprises potassium permanganate, sodium permanganate, lithium permanganate, calcium permanganate, manganese sulfate, manganese chloride, manganese nitrate, manganese perchlorate, manganese acetate, manganese bis(trifluoromethanesulfonate), manganese trifluoromethanesulfonate, manganese carbonate, manganese oxalate, manganese fluorosilicate, manganese ferrocyanide, manganese bromide, magnesium sulfate, ammonium chloride, ammonium sulfate, ammonium hydroxide, zinc sulfate, zinc trifluoromethanesulfonate, zinc acetate, zinc nitrate, bismuth chloride, bismuth nitrate, nitric acid, Sulfuric acid, hydrochloric acid, sodium sulfate, potassium sulfate, 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, carboxymethyl cellulose, xanthan gum, carrageenan, acrylamide, potassium persulfate, sodium persulfate, ammonium persulfate, N,N'-methylenebisacrylamide, or a combination thereof.

[0153] A thirty-second embodiment may include the cell of the thirtieth or thirty-first embodiment, wherein the polymeric catholyte solution has a pH between -1.2 and 7.

[0154] A thirty-third embodiment may include the battery of any of the thirtieth through thirty-second embodiments, wherein the polymeric catholyte solution comprises lead sulfate and ammonium chloride at concentrations between 0 and 10 M.

[0155] A thirty-fourth embodiment may include the cell of any of the thirtieth through thirty-third embodiments, wherein the polymeric catholyte solution comprises sulfuric acid, hydrochloric acid, or nitric acid at a concentration between 0 and 16 M.

[0156] A thirty-fifth embodiment may include the battery of any of embodiments 30 through 34, wherein the polymeric cathode electrolyte solution comprises lead sulfate, ammonium chloride, and an acid, wherein the molar ratio of the mixture of lead sulfate and ammonium chloride to the acid is from 0.1:5 to 5:0.1.

[0157] A thirty-sixth embodiment may include the battery of any one of the thirtieth to thirty-fifth embodiments, wherein the cathode further comprises carbon mixed with lead oxide (PbO2).

[0158] A thirty-seventh embodiment may include the battery of the thirty-sixth embodiment, wherein the amount of lead oxide (PbO 2 ) is between 1 and 99 wt. %, and the amount of carbon is between 1 and 99 wt. %.

[0159] A thirty-eighth embodiment may include the cell of any of the thirtieth through thirty-seventh embodiments, wherein the polymeric anolyte solution has a pH between 7 and 15.13.

[0160] In a thirty-ninth embodiment, a method of operating a battery includes: discharging the battery according to any one of the first to thirty-eighth embodiments; and, after the battery is discharged, charging the battery.

[0161] A fortieth embodiment may include the method of the thirty-ninth embodiment, wherein the battery is charged a plurality of times.

[0162] A forty-first embodiment may include the method of the thirty-eighth or fortieth embodiment, wherein the battery is discharged at a voltage between 2V and 3.6V.

[0163] Embodiments are discussed herein with reference to the accompanying drawings. However, those skilled in the art will readily appreciate that the detailed description given herein with respect to these drawings is for explanatory purposes and that the systems and methods extend beyond these limited embodiments. For example, it will be understood that, in view of the teachings of this specification, those skilled in the art will recognize a variety of alternative and suitable methods of implementing the functionality of any given detail described herein, in addition to the specific implementation choices in the embodiments described and illustrated below, as needed for a particular application. That is, there are a large number of modifications and variations that are too numerous to list, but are within the scope of this specification. Furthermore, where appropriate, words in the singular shall be construed as plural and vice versa, words in the masculine shall be construed as feminine and vice versa, and alternative embodiments do not necessarily mean that the two are mutually exclusive.

[0164] It should be further understood that this specification is not limited to the specific methods, compounds, materials, manufacturing techniques, uses and applications described herein, as these are all variable. It should also be understood that the terms used herein are only used to describe the purpose of specific embodiments and are not intended to limit the scope of this system and method. It must be noted that, as used herein and in the appended claims (in this application or any derivative thereof), unless the context clearly stipulates otherwise, the singular forms "a", "an" and "the" include plural references. Therefore, for example, a reference to "an element" is a reference to one or more elements and includes equivalents known to those skilled in the art. All conjunctions used should be understood in the broadest sense as much as possible. Therefore, unless the context clearly requires, the word "or" should be understood to have a logical "or" definition, rather than a logical "exclusive or" definition. The structure described herein should also be understood to refer to the functional equivalent of this structure. Unless the context clearly stipulates otherwise, the language constituting the expression "approximately" should also be understood in this way.

[0165] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this specification belongs. Although any methods, techniques, devices, or materials similar or equivalent to those described herein may be used in the practice or testing of the present systems and methods, preferred methods, techniques, devices, and materials are described. The structures described herein are also understood to refer to functional equivalents of such structures. The present systems and methods will now be described in detail with reference to the embodiments shown in the accompanying drawings.

[0166] From reading this application, other variations and modifications will be apparent to those skilled in the art.Such variations and modifications may involve equivalent and other features that are already known in the art and that may be used to replace or supplement the features already described herein.

[0167] Although the claims may be constructed in this application or any other application derived therefrom to specific combinations of features, it should be understood that the scope of this application also includes any novel feature or any novel combination of features disclosed explicitly or implicitly herein, or any generalization thereof, whether or not it relates to the same system or method as currently claimed in any claim and whether or not it alleviates any or all of the same technical problems as the present system and method.

[0168] Features described in the context of different embodiments may also 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 also be provided individually or in any suitable subcombination. Applicants hereby clarify that new claims may be formulated to such features and / or combinations of such features during the course of this application or any further applications derived therefrom.

Claims

1. A high-voltage aqueous battery comprising: a cathode comprising a cathode electroactive material adhered to a cathode current collector in the form of a paste layer, wherein the cathode electroactive material comprises manganese dioxide; an anode comprising an anode electroactive material disposed in contact with an anode current collector, wherein the anode electroactive material comprises zinc; an acidic to neutral catholyte solution in contact with the cathode electroactive material, wherein the catholyte solution is not in contact with the anode electroactive material; and An alkaline polymeric anolyte solution is in contact with the anode electroactive material.

2. The high-voltage aqueous battery according to claim 1, wherein: The anode further includes iron oxide, iron hydroxide, bismuth oxide, bismuth, indium oxide, indium hydroxide, indium, copper, copper oxide, copper hydroxide, manganese oxide, or any combination thereof.

3. The high-voltage aqueous battery according to claim 1, wherein: The cathode and the anode each include a current collector made of carbon, lead, copper, nickel, silver, bismuth, titanium, magnesium, aluminum, gold, or a combination thereof.

4. The high-voltage aqueous battery according to claim 3, wherein: The current collector is a mesh, foil, foam, felt, fiber, porous monolithic structure, or a combination thereof.

5. The high-voltage aqueous battery according to claim 1, wherein: The cathode electrolyte solution comprises potassium permanganate, sodium permanganate, lithium permanganate, manganese sulfate, manganese chloride, manganese nitrate, manganese perchlorate, manganese acetate, manganese bis(trifluoromethanesulfonate), manganese trifluoromethanesulfonate, manganese carbonate, manganese oxalate, manganese fluorosilicate, manganese ferrocyanide, manganese bromide, magnesium sulfate, zinc sulfate, zinc trifluoromethanesulfonate, zinc acetate, zinc nitrate, bismuth chloride, bismuth nitrate, nitric acid, sulfuric acid, hydrochloric acid, sodium sulfate, potassium sulfate, sodium hydroxide, potassium hydroxide, titanium sulfate, titanium chloride, lithium nitrate, lithium chloride, lithium bromide, lithium bicarbonate, lithium acetate, lithium sulfate, lithium nitrite, lithium hydroxide, lithium perchlorate, lithium oxalate, lithium fluoride, lithium carbonate, lithium bromate, or a combination thereof.

6. The high-voltage aqueous battery according to claim 1, wherein: The catholyte solution has a pH of -1.2 to 7.

7. The high-voltage aqueous battery according to claim 1, wherein: The catholyte solution comprises permanganate at a concentration greater than 0 and less than or equal to 5M.

8. The high-voltage aqueous battery according to claim 1, wherein: The cathode electrolyte solution comprises potassium permanganate at a concentration greater than 0 and less than or equal to 5M.

9. The high-voltage aqueous battery according to claim 1, wherein: The cathode electrolyte solution comprises sulfuric acid, hydrochloric acid or nitric acid at a concentration greater than 0 and less than or equal to 16M.

10. The high-voltage aqueous battery according to claim 1, wherein: The catholyte solution comprises permanganate and an acid, wherein the molar ratio of the permanganate to the acid is 1:

3.

11. The high-voltage aqueous battery according to claim 1, wherein: The cathode electrolyte solution comprises potassium permanganate and an acid, wherein the molar ratio of the potassium permanganate to the acid is 1:

3.

12. The high-voltage aqueous battery according to claim 1, wherein: The cathode electroactive material comprises manganese dioxide mixed with carbon.

13. The high-voltage aqueous battery according to claim 12, wherein: The carbon is graphite, carbon fiber, carbon black, acetylene black, single-walled carbon nanotubes, multi-walled carbon nanotubes, nickel- or copper-coated carbon nanotubes, a dispersion of single-walled carbon nanotubes, a dispersion of multi-walled carbon nanotubes, graphene, graphyne, graphene oxide, or a combination thereof.

14. The high-voltage aqueous battery according to claim 1, wherein: The polymeric anolyte solution comprises 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 nitrite, lithium perchlorate, lithium oxalate, lithium fluoride, lithium carbonate, lithium bromate, acrylic acid, N,N'-methylenebisacrylamide, potassium persulfate, ammonium persulfate, sodium persulfate, or a combination thereof.

15. The high-voltage aqueous battery according to claim 1, wherein: The polymeric anolyte solution has a pH of 10 to 15.

13.

16. The high-voltage aqueous battery according to claim 1, wherein: The anode is a foil structure, a mesh structure, a perforated structure, a foam structure, a felt structure or a powder structure.

17. The high-voltage aqueous battery according to claim 1, further comprising: A separator is disposed between the catholyte solution and the polymeric anolyte solution.

18. The high-voltage aqueous battery according to claim 17, wherein: The separator is polyvinyl alcohol, a composite of polyvinyl alcohol and graphene oxide, a microporous separator, a cellulose membrane, or a combination thereof.

19. The high-voltage aqueous battery according to claim 1, wherein: The catholyte solution is polymeric.

20. The high-voltage aqueous battery according to claim 1, wherein: The battery has an open circuit potential of 2V to 4V.

21. A high-voltage aqueous battery comprising: a cathode comprising a cathode electroactive material, wherein the cathode electroactive material comprises manganese dioxide, spinel manganese oxide, or manganese oxide, and wherein the cathode electroactive material is adhered to a cathode current collector in the form of a paste layer; an anode comprising an anode electroactive material, wherein the anode electroactive material comprises zinc and the anode electroactive material is disposed in contact with an anode current collector; an acidic to neutral polymeric catholyte solution in contact with the cathodic electroactive material and not in contact with the cathodic electroactive material; and An alkaline polymeric anolyte solution is in contact with the anode electroactive material.

22. The high-voltage aqueous battery according to claim 21, wherein: The polymeric cathode electrolyte solution comprises manganese sulfate, ammonium chloride, ammonium sulfate, manganese acetate, and permanganate at a concentration greater than 0 and less than or equal to 10M.

23. The high-voltage aqueous battery according to claim 21, wherein: The polymeric catholyte solution comprises manganese sulfate, ammonium chloride, ammonium sulfate, manganese acetate or potassium permanganate at a concentration greater than 0 and less than or equal to 10M.

24. The high-voltage aqueous battery according to claim 21, wherein: The polymeric catholyte solution comprises sulfuric acid, hydrochloric acid or nitric acid at a concentration greater than 0 and less than or equal to 16M.

25. The high-voltage aqueous battery according to claim 21, wherein: The polymeric catholyte solution comprises permanganate and an acid; wherein the volume ratio of the permanganate to the acid is 5:1 to 1:

5.

26. The high-voltage aqueous battery according to claim 21, wherein: The polymeric catholyte solution comprises potassium permanganate and an acid; wherein the volume ratio of the potassium permanganate to the acid is 5:1 to 1:

5.

27. The high-voltage aqueous battery according to claim 21, wherein: The polymeric catholyte solution comprises manganese sulfate, ammonium chloride, and acid, wherein the volume ratio of the mixture of manganese sulfate and ammonium chloride to the acid is 5:1 to 1:

5.

28. The high-voltage aqueous battery according to claim 21, wherein: The manganese dioxide is mixed with carbon.

29. The high-voltage aqueous battery according to claim 28, wherein: The mixture of manganese dioxide and carbon further comprises cobalt oxide, cobalt hydroxide, lead oxide, lead hydroxide, or a combination thereof.

30. A high-voltage aqueous battery comprising: a cathode comprising a cathode electroactive material, wherein the cathode electroactive material comprises manganese dioxide (MnO2), and the cathode electroactive material is adhered to a cathode current collector in the form of a paste layer; an anode comprising an anode electroactive material, wherein the anode electroactive material comprises zinc and the anode electroactive material is disposed in contact with an anode current collector; an acidic to neutral polymeric catholyte solution in contact with the cathodic electroactive material and not in contact with the cathodic electroactive material; and An alkaline polymeric anolyte solution is in contact with the anode electroactive material.

31. The high-voltage aqueous battery according to claim 30, wherein: The polymeric cathode electrolyte solution comprises potassium permanganate, sodium permanganate, lithium permanganate, calcium permanganate, manganese sulfate, manganese chloride, manganese nitrate, manganese perchlorate, manganese acetate, manganese bis(trifluoromethanesulfonate), manganese trifluoromethanesulfonate, manganese carbonate, manganese oxalate, manganese fluorosilicate, manganese ferrocyanide, manganese bromide, magnesium sulfate, ammonium chloride, ammonium sulfate, ammonium hydroxide, zinc sulfate, zinc trifluoromethanesulfonate, zinc acetate, zinc nitrate, bismuth chloride, bismuth nitrate, nitric acid, sulfuric acid, hydrochloric acid, sodium sulfate, potassium sulfate, cobalt sulfate, lead sulfate, sodium hydroxide, potassium hydroxide, titanium sulfate, titanium chloride, 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 bromate, polyvinyl alcohol, carboxymethyl cellulose, xanthan gum, carrageenan, acrylamide, potassium persulfate, sodium persulfate, ammonium persulfate, N,N'-methylenebisacrylamide, or a combination thereof.

32. The high-voltage aqueous battery according to claim 30, wherein: The polymeric catholyte solution has a pH of -1.2 to 7.

33. The high-voltage aqueous battery according to claim 30, wherein: The polymeric catholyte solution comprises lead sulfate and ammonium chloride at a concentration greater than 0 and less than or equal to 10M.

34. The high-voltage aqueous battery according to claim 30, wherein: The polymeric catholyte solution comprises sulfuric acid, hydrochloric acid or nitric acid at a concentration greater than 0 and less than or equal to 16M.

35. The high-voltage aqueous battery according to claim 30, wherein: The polymeric catholyte solution comprises lead sulfate, ammonium chloride, and an acid, wherein the molar ratio of the mixture of lead sulfate and ammonium chloride to the acid is from 0.1:5 to 5:0.

1.

36. The high-voltage aqueous battery according to claim 30, wherein: The cathode further comprises carbon mixed with PbO2.

37. The high-voltage aqueous battery according to claim 36, wherein: The amount of the manganese dioxide (MnO 2 ) is 1 wt. % to 99 wt. %, and the amount of the carbon is 1 wt. % to 99 wt. %.

38. The high-voltage aqueous battery according to claim 30, wherein: The polymeric anolyte solution has a pH of 7 to 15.13.

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