Bicathodic method to improve energy density of metal-based batteries

Abstract

The present application relates to a dual electrolyte battery comprising a cathode, an anode, a cathode electrolyte in contact with the cathode, and an anode electrolyte in contact with the anode. The cathode electrolyte comprises a first gel electrolyte solution, and the anode electrolyte comprises a second gel electrolyte solution. The electrolyte concentration in the anode electrolyte is higher than the electrolyte concentration in the cathode electrolyte.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Application 62 / 953,674, filed December 26, 2019, entitled “A dual-electrolyte method for improving the energy density of aqueous metal-based batteries,” the entire contents of which are incorporated herein by reference for all purposes.

[0003] Statement regarding government-funded research or development

[0004] none Background Technology

[0005] Applications such as power grids, electric vehicles, solar cells, and uninterruptible power supplies all require energy storage systems like batteries. Lithium-ion and lead-acid batteries currently dominate the market; however, they are expensive, flammable, and contain toxic elements. Aqueous-based metal anode systems, such as zinc (Zn) anode batteries, can compete with lithium and lead in terms of volumetric and gravimetric energy density. These batteries are typically sold as primary batteries because their active materials are irreversible after complete discharge and can only be used once. Summary of the Invention

[0006] In some embodiments, the dual-electrolyte battery includes a cathode, an anode, a cathode electrolyte in contact with the cathode, and an anode electrolyte in contact with the anode. The cathode electrolyte includes a first gel electrolyte solution, and the anode electrolyte includes a second gel electrolyte solution. The electrolyte concentration in the anode electrolyte is higher than the electrolyte concentration in the cathode electrolyte.

[0007] In some embodiments, the dual-electrolyte battery includes a cathode, an anode, a cathode electrolyte in contact with the cathode, and an anode electrolyte in contact with the anode. The cathode electrolyte includes a first gel electrolyte solution, and the anode electrolyte includes a second gel electrolyte solution. Both the first and second gel electrolyte solutions include hydroxides, and the concentration of hydroxides in the anode electrolyte is higher than the concentration of hydroxides in the cathode electrolyte.

[0008] In some embodiments, a method of forming a dual-electrolyte battery includes: providing a cathode electrolyte in contact with the cathode, providing an anode electrolyte in contact with the anode, and providing at least one separator or buffer layer between the anode electrolyte and the cathode electrolyte. The cathode electrolyte includes a first gel electrolyte solution, and the anode electrolyte includes a second gel electrolyte solution. The concentration of hydroxide in the anode electrolyte is higher than the concentration of hydroxide in the cathode electrolyte.

[0009] These and other features will become clearer from the following detailed description in conjunction with the appended claims. Attached Figure Description

[0010] This disclosure and its advantages will now be understood more fully with reference to the following brief and detailed description taken in conjunction with the accompanying drawings, wherein like reference numerals denote like parts.

[0011] Figure 1 The graph shows the relationship between the ionic conductivity of zinc powder, zinc oxide solubility, and degassing rate and the concentration of KOH.

[0012] Figure 2 The open-circuit voltage (OCV) of the MnO2 and Zn electrodes is shown at different KOH concentrations.

[0013] Figures 3A to 3D A schematic diagram of a dual-electrolyte MnO2|zinc battery according to some embodiments is shown.

[0014] Figure 4 The graph shows the change in KOH concentration after the polymerization process. Neutralization with acrylic acid reduced the KOH concentration.

[0015] Figure 5 The gelation time is shown for different KOH concentrations.

[0016] Figure 6 The potential-time curves of a MnO2 electrode cycled in a 10% KOH aqueous solution at 40% utilization of its theoretical single-electron capacity (308 mAh / g) are shown.

[0017] Figure 7 The potential-time curves of a zinc electrode circulated in a PGE are shown.

[0018] Figure 8 The full-cell discharge performance is shown in a low-concentration PGE cathode with MnO2 and a high-concentration PGE with Zn anode, achieving 100% of the theoretical single-electron capacity (308 mAh / g).

[0019] Figure 9 The full-cell cycling performance is shown for a MnO2 cathode in low-concentration PGE and a Zn porous anode in high-concentration PGE that achieves 40% of the theoretical single-electron capacity (308 mAh / g).

[0020] Figure 10 The full-cell cycling performance is shown in a low-concentration PGE mixed with graphite cathode and a Zn anode in a high-concentration PGE that achieves 40% of the theoretical single-electron capacity (308 mAh / g).

[0021] Figure 11The full-cell cycling performance is shown in a MnO2 cathode in low-concentration PGE and a Zn mesh anode in high-concentration PGE, achieving 40% of the theoretical single-electron capacity (308 mAh / g). Detailed Implementation

[0022] In this disclosure, the terms "negative electrode" and "anode" are used to refer to a "negative electrode." Similarly, the terms "positive electrode" and "cathode" are used to refer to a "positive electrode." The term "electrode" alone may refer to the anode, cathode, or both. The term "primary battery" (e.g., "primary battery," "primary electrochemical cell," or "primary cell") refers to a cell or battery that is disposed of and replaced after a single discharge. The term "secondary battery" (e.g., "secondary battery," "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, "cathode electrolyte" refers to an electrolyte solution that is in contact with the cathode but not in direct contact with the anode, and "anode electrolyte" refers to an electrolyte solution that is in contact with the anode but not in direct contact with the cathode. The term "electrolyte" alone may refer to the cathode electrolyte, the anode electrolyte, or an electrolyte that is in direct contact with both the anode and cathode.

[0023] Applications such as power grids, electric vehicles, solar cells, and uninterruptible power supplies all require energy storage systems like batteries. Lithium-ion and lead-acid batteries currently dominate the market; however, they are expensive, flammable, and contain toxic elements. Aqueous-based metal anode systems, such as zinc (Zn) anode batteries, when paired with inexpensive and abundant cathode materials, such as manganese dioxide (MnO2), can compete with lithium and lead in terms of volumetric and gravimetric energy density. These batteries can release >400 Wh / L in aqueous alkaline electrolytes. High energy density is possible because MnO2 and Zn have high theoretical capacities, based on first and second electron reactions of approximately 617 mAh / g and approximately 820 mAh / g, respectively.

[0024] When attempting to achieve maximum utilization, irreversible problems arise, such as volume expansion, disruption of the spinel crystal structure, redistribution of active materials, zinc poisoning of the anode, passivation of the metal cathode, and dendritic short circuits. The electrolyte, potassium hydroxide (KOH), is a source of some of these problems. During discharge, 4 + The price of Mn decreased to 3 + The valence of this leads to increased solubility of Mn at high KOH concentrations with high capacity utilization. 3+ The loss of ions is the cause of capacity loss in the battery. Simultaneously, dissolved Mn... 3+ Ions can also dissociate to form Mn 4+ and Mn 2+This leads to the formation of lower oxides (e.g., spinel Mn3O4) and hydroxymanganese oxide [Mn(OH)2]. Zinc ions are formed when dissolved zincate ions [Zn(OH)4] are present. 2- The reaction becomes more complex when the zincate ions dissolve to release their capacity. These dissolved zincate ions also react with dissolved Mn ions to form inactive Zn spinels, such as ZnMn₂O₄. Zn anodes can also form dendrites during charging, and these dendrites can penetrate the separator and short-circuit the battery.

[0025] Another problem with Zn anodes is the redistribution of active material during the dissolution reaction, which leads to the loss of active ions in the current collector, resulting in capacity loss. The cathode also experiences significant volume expansion during its discharge reaction as protons from the electrolyte insert into the crystal structure, causing active material to peel off from the current collector, resulting in further capacity loss.

[0026] This disclosure discloses methods and steps for preparing KOH-containing polymeric gel electrolytes (PGEs) within a framework tailored to the corresponding electrodes in terms of concentration, viscosity, and ionic conductivity. The fabrication of PGEs enables the use of two electrolyte concentrations in a single cell, which are adjusted to obtain improved or optimal cathode and anode performance, respectively.

[0027] More specifically, the batteries and methods disclosed herein can utilize polymer gel electrolytes (PGEs) with different concentrations on both the cathode and anode sides, wherein the properties of the PGEs are tuned to achieve improved utilization of the respective electrodes. The MnO2 cathode is preferably gelled at a low KOH concentration to limit Mn. 3+ The solubility of Zn ions is a key factor, and the Zn anode is preferably gelled at high KOH concentrations to increase the solubility of Zn ions, as capacity utilization depends on the solubility of Zn. Other additives, such as carbon, Teflon, and cellulose fibers, can also be added to the PGE to improve the electrode's capacity utilization and limit gas trapping in the gel. Furthermore, the viscosity of the PGE used for the anode can be lower than that used for the cathode. This allows any escaping gases at the anode to migrate away from the anode, while the higher viscosity in the cathode restricts the migration of any manganese ions from the cathode and the entry of any zincate ions into the cathode.

[0028] In some embodiments, a cell is disclosed having a first PGE of concentration A applied to the cathode and a second PGE of concentration B applied to the anode side. A separator or buffer layer may be present between the PGEs to prevent mixing. The PGE of concentration A on the cathode side may be lower, while the PGE of concentration B on the anode side may be higher. In some aspects, the viscosity of the PGE of concentration A may be higher than the viscosity of the PGE of concentration B on the anode side.

[0029] refer to Figure 1 This section explains the rationale behind the design of this dual-electrolyte battery. Generally, the zinc anode releases its capacity through a dissolution mechanism, making the solubility of zinc ions in the electrolyte crucial. However, the zinc anode corrodes in hydroxide electrolytes such as KOH, releasing hydrogen. During battery operation, the emission of this gas is important for either release into the atmosphere or reaction with the catalyst within the battery to re-form water. The viscosity of the PGE on the anode side can then be adjusted to allow Zn dissolution and hydrogen escape. An electrolyte with a higher hydroxide concentration can also be used to allow more zinc to dissolve in the PGE on the anode side, thereby improving capacity utilization. The hydroxide concentration in the cathode-side electrolyte can be reduced to limit the solubility of Mn in the PGE while still maintaining a high single-electrode capacity utilization; and the viscosity of the PGE on the cathode side should be sufficiently high to limit the diffusion of zincate ions from the anode side to the cathode side.

[0030] Another advantage of dual-electrolyte batteries is the lower alkaline concentration of PGE on the cathode side and the higher alkaline concentration on the anode side, which increases the battery potential, such as Figure 2 As shown, a lower alkali concentration on the cathode side and a higher alkali concentration on the anode side can increase the battery potential, thereby resulting in a higher average discharge voltage and thus higher battery energy.

[0031] Reference Figures 3A to 3D The battery 10 may have a casing 7, a cathode 12, and an anode 13. 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. Note that... Figures 3A to 3D The proportions of the components may not be precise because these features are shown to clearly show the electrolyte around the anode 13 and cathode 12. Figures 3A to 3C A prismatic battery device with a single anode 13 and cathode 12 is shown. In another embodiment, the battery may be a cylindrical battery with concentrically arranged electrodes (e.g., as shown in the diagram). Figure 3D (As shown), or a wound structure in which the anode and cathode are layered and then wound to form a rolled structure. The cathode current collector 1 and the cathode material 2 are collectively referred to as cathode 12 or positive electrode 12, such as Figure 2 As shown. Similarly, the anode material 5 having the optional anode current collector 4 can be collectively referred to as anode 13 or negative electrode 13. The electrolyte can contact the cathode 12 and anode 13. As described in more detail herein, in some embodiments, the electrolyte 15 in contact with both the cathode 12 and anode can be the same electrolyte at different concentrations, or alternatively, different electrolyte compositions can be used with the anode 13 and cathode 12 to adjust the performance of the battery 10.

[0032] In some embodiments, the battery 10 may include one or more cathodes 12 and one or more anodes 13, which may be present in any configuration or shape factor. When multiple anodes 13 and / or multiple cathodes 12 are present, the electrodes may be configured in a layered structure such that 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 coil configuration (e.g., as shown in the image), Figure 3D As shown), the battery 10 may have only one cathode 12 and one anode 13 in the winding structure, such that the cross-section of the battery 10 includes a layered structure of alternating electrodes, although multiple cathodes 12 and anodes 13 may also be used in the layered structure and wound to form a winding structure with alternating layers.

[0033] In one embodiment, the housing 7 includes a molded box or container that is generally non-reactive with respect to the electrolyte solution (including the electrolyte) in the battery 10. In one embodiment, the housing 7 includes a polymer (e.g., a polypropylene molded box, an acrylic polymer molded box, etc.), coated metal, etc.

[0034] Cathode 12 may include a mixture of components containing electrochemically active materials. Optionally, it may also include additional components, such as binders, conductive materials, and / or one or more additional components, to improve the lifetime, rechargeability, and electrochemical performance of cathode 12. Cathode 12 may include cathode material 2 (e.g., electroactive materials, additives, etc.). The cathode may contain about 1 wt% to about 95 wt% of active material. Suitable cathode material 2 may include, but is not limited to, manganese dioxide, copper manganese oxide, permanganate, manganese oxide, copper-intercalated bismuth hydrate, bismuth hydrate, todokorite, orthorhombic manganese oxide, pyrochroite, silver oxide, silver dioxide, silver, nickel hydroxide, nickel, lead oxide, copper oxide, copper dioxide, lead, lead dioxide (α and β), potassium persulfate, sodium persulfate, ammonium persulfate, potassium permanganate, calcium permanganate, barium permanganate, silver permanganate, ammonium permanganate, peroxide, gold, perchlorate, cobalt oxide (CoO2). The cathode may contain: (CoO2, Co3O4), lithium cobalt oxide, sodium cobalt oxide, perchlorate, nickel oxide, bromine, mercury, vanadium oxide, vanadium bismuth oxide, hydroquinone, calix[4]quinone, tetrachlorobenzoquinone, 1,4-naphthoquinone, 9,10-anthraquinone, 1,2-naphthoquinone, 9,10-phenanthroquinone, nitrogen oxides-ammonium oxide cation redox pairs (e.g., (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO)), carbon, 2,3-dicyano-5,6-dichlorodicyanoquinone, tetracyanoethylene, sulfur trioxide, ozone, oxygen, air, lithium nickel manganese cobalt oxide, sulfur, lithium iron phosphate, copper lithium oxide, copper oxyphosphate, or any combination thereof. In some embodiments, the cathode may include an air electrode.

[0035] In some embodiments, the cathode material 2 may be one or more polymorphs based on MnO2, including electrolytic MnO2 (EMD), α-MNO2, β-MNO2, γ-MNO2, δ-MNO2, ε-MNO2, or λ-MNO2. Other forms of MnO2 may also exist, such as hydrated MnO2, pyrolusite, naphthosite, manganese barium ore, barium pyrolusite, barium magnesium manganese ore, lithium tremolite, chalcopyrite, sodium- or potassium-rich naphthosite, manganese potassium ore, magnesium alkali manganese ore, manganese hydroxyoxide (MnOOH), α-MnOOH, γ-MnOOH, β-MnOOH, manganese hydroxide [Mn(OH)2], partially or fully protonated manganese dioxide, Mn3O4, Mn2O3, ferromanganese, MnO, lithium-ionized manganese dioxide (LiMn2O4, Li2MnO3), CuMn2O4, aluminum manganese oxide, zinc manganese dioxide, bismuth manganese oxide, copper-intercalated naphthosite, copper-intercalated bismuth naphthosite, tin-doped manganese oxide, magnesium manganese oxide, or any combination thereof. Generally, the circulating form of manganese dioxide in the cathode can have a layered structure, and in some embodiments, the layered structure can include δ-MNO2, which is interchangeably referred to as naphthoic manganese dioxide. If non-naphthoic manganese dioxide polymorphs are used, these can be converted to naphthoic manganese dioxide in situ by one or more controlled cycles, as described in more detail below. For example, a complete or partial discharge of manganese dioxide at the end of its second electron phase can be performed (e.g., between approximately 20% and approximately 100% of the second electron capacity of the cathode), followed by recharging back to its Mn content. 4+ The valence state is thus changed, resulting in the formation of manganese dioxide in the sodium manganese ore phase.

[0036] The addition of conductive additives (such as conductive carbon) allows for a high loading of electroactive materials in the cathode material, resulting in high volumetric and gravimetric energy densities. In some embodiments, the conductive additives may include graphite, carbon fibers, carbon black, acetylene black, single-walled carbon nanotubes, multi-walled carbon nanotubes, nickel- or copper-coated carbon nanotubes, single-walled carbon nanotube dispersions, multi-walled carbon nanotube dispersions, graphene, graphyne, graphene oxide, or combinations thereof. In some embodiments, a higher loading of electroactive materials in the cathode is desirable 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-walled or multi-walled), Zenyatta graphite, and / or combinations thereof.

[0037] In some embodiments, the conductive additive may have a particle size range of about 1 to about 50 micrometers, or about 2 to about 30 micrometers, or about 5 to about 15 micrometers. The total mass percentage of the conductive additive in the cathode material 2 may be about 5% to about 99%, or about 10% to about 80%. In some embodiments, the electroactive component in the cathode material 2 may be from 1 wt% to 99 wt% of the weight of the cathode material 2, and the conductive additive may be from 1 wt% to 99 wt%.

[0038] The cathode material 2 may also include a conductive component. Adding a conductive component, such as a metal additive, to the cathode material 2 can be accomplished by adding one or more metal powders (such as nickel powder) to the cathode material 2. The conductive metal component may be present in the cathode material 2 at a concentration 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 oxides and / or salts. 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 as a supporting conductive framework for the occurrence of the first and second electronic reactions. The second electronic reaction has a dissolution-precipitation reaction, wherein Mn3+ Ions become soluble in the electrolyte and precipitate on materials such as graphite, leading to an electrochemical reaction and the formation of non-conductive manganese hydroxide [Mn(OH)₂]. This ultimately results in capacity decay in subsequent cycles. Suitable conductive components that can help reduce the solubility of manganese ions include transition metals such as Ni, Co, Fe, and Ti, and metals such as Ag, Au, Al, and Ca. Oxides and salts of these metals are also suitable. Transition metals, such as Co, also help reduce the solubility of Mn. 3+ Solubility of ions. These conductive metal components can be incorporated into the electrode by chemical or physical methods (e.g., ball milling, mortar / pestle, Spex mixture). Examples of such electrodes include 5% to 95% sodium manganese hydrate, 5% to 95% conductive carbon, 0% to 50% conductive components (e.g., conductive metals), and 1% to 10% binder.

[0039] In some embodiments, the adhesive can be used with the cathode material 2. The adhesive can be present at a concentration of about 0 wt% to 10 wt% of the cathode material, or alternatively at a concentration of about 1 wt% to 5 wt%. In some embodiments, the adhesive comprises a water-soluble cellulose-based hydrogel, which can be used as a thickener and strong adhesive, and has been crosslinked with good mechanical strength and conductive polymers. The adhesive can also be a cellulose film sold as cellophane. The adhesive is prepared by physically crosslinking the water-soluble cellulose-based hydrogel with the polymer through repeated cooling and thawing cycles. In some embodiments, the adhesive can comprise a 0 wt% to 10 wt% carboxymethyl cellulose (CMC) solution crosslinked with an equal volume of 0 wt% to 10 wt% polyvinyl alcohol (PVA). This adhesive exhibits superior performance compared to conventionally used PTFE (polytetrafluoroethylene). PTFE is a highly resistive material, but it is widely used in industry due to its good flexibility. However, this does not preclude the use of PTFE as an adhesive. Mixtures of PTFE with aqueous adhesives and some conductive carbon have been used to manufacture flexible adhesives. Using a water-based binder helps achieve most of the two-electron capacity with minimal capacity loss over multiple cycles. In some embodiments, the binder may be water-based, possessing excellent water retention, adhesive properties, and helping to maintain conductivity relative to the same cathode using a PTFE binder. Examples of suitable water-based hydrogels include, but are not limited to, methylcellulose (MC), carboxymethylcellulose (CMC), hydroxypropylcellulose (HPH), hydroxypropyl methylcellulose (HPMC), hydroxyethyl methylcellulose (HEMC), carboxymethyl hydroxyethylcellulose, hydroxyethyl cellulose (HEC), and combinations thereof. Examples of crosslinking polymers include polyvinyl alcohol, polyvinyl acetate, polyaniline, polyvinylpyrrolidone, polyvinylidene fluoride, polypyrrole, and combinations thereof. In some embodiments, a 0 wt% to 10 wt% water-based cellulose hydrogen solution is crosslinked with a 0 wt% to 10 wt% crosslinking polymer solution by, for example, repeated freeze / thaw cycles, radiation treatment, and / or chemical agents (e.g., epichlorohydrin). The water-based binder may be mixed with 0% to 5% PTFE to improve manufacturability.

[0040] Cathode material 2 may also contain additional elements. These additional elements include bismuth compounds and / or copper / copper compounds, which can be included in the cathode material to improve the galvanostatic cycle performance of the cathode. When present as naphthoic mineral, copper and / or bismuth can be incorporated into the layered nanostructure of naphthoic mineral. Because copper and bismuth are incorporated into the crystal and nanostructure of naphthoic mineral, the resulting naphthoic mineral cathode material can exhibit improved cycling and long-term performance.

[0041] Bismuth compounds may be incorporated into the cathode 12 in the form of inorganic or organic salts of bismuth (oxidation states 5, 4, 3, 2, or 1), bismuth oxides, or bismuth metal (i.e., elemental bismuth). The bismuth compounds may be present in the cathode material at a concentration of about 1 wt% to 20 wt% of the cathode material 2 by weight. Examples of bismuth compounds include bismuth chloride, bismuth bromide, bismuth fluoride, bismuth iodide, bismuth sulfate, bismuth nitrate, bismuth trichloride, bismuth citrate, bismuth telluride, bismuth selenide, bismuth hyposalicylate, bismuth neodecanoate, bismuth carbonate, bismuth hypogallate, bismuth strontium calcium copper oxide, bismuth acetate, bismuth trifluoromethanesulfonate, bismuth oxide nitrate, 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 antimony, bismuth antimony telluride, stabilized bismuth oxide yttrium, bismuth-lead alloy, bismuth ammonium citrate, 2-naphthol bismuth salt, duchloritri(o-tolyl)bismuth, dichlorodiphenyl(p-tolyl)bismuth, triphenylbismuth, and / or combinations thereof.

[0042] Copper compounds can be incorporated into the cathode 12 in the form of organic or inorganic salts of copper (oxidation states 1, 2, 3, or 4), copper oxides, or metallic copper (i.e., elemental copper). The copper compound can be present at a concentration of about 1 wt% to 70 wt% of the cathode material 2 by weight. In some embodiments, the copper compound is present at a concentration of about 5 wt% to 50 wt% of the cathode material 2 by weight. In other embodiments, the copper compound is present at a concentration of about 10 wt% to 50 wt% of the cathode material 2 by weight. In yet another embodiment, the copper compound is present at a concentration of about 5 wt% to 20 wt% of the cathode material 2 by weight. Examples of copper compounds include copper and copper salts, such as copper aluminum oxides, copper (I) oxides, copper (II) oxides, and / or copper salts in oxidation states +1, +2, +3, or +4, including but not limited to copper nitrate, copper sulfate, copper chloride, etc. The role of copper is to alter the oxidation and reduction voltage of bismuth. This makes the cathode fully reversible during constant current cycling, compared to bismuth-modified MnO2, which cannot withstand constant current cycling.

[0043] The cathode 12 can be produced using methods capable of being implemented in large-scale manufacturing. For the MnO2 cathode, the cathode 12 is capable of delivering the full second electron capacity of MnO2. In some embodiments, the cathode material 2 may comprise 2 wt% to 30 wt% conductive carbon, 0 wt% to 30 wt% conductive metal additives, 1 wt% to 70 wt% copper compound, 1 wt% to 20 wt% bismuth compound, 0 wt% to 10 wt% binder, and naphthoic mineral or EMD. In another embodiment, the cathode material comprises 2 wt% to 30 wt% conductive carbon, 0 wt% to 30 wt% conductive metal additives, 1 wt% to 20 wt% bismuth compound, 0 wt% to 10 wt% binder, and naphthoic mineral or EMD. In one embodiment, the cathode material is substantially composed of 2 wt% to 30 wt% conductive carbon, 0 wt% to 30 wt% conductive metal additives, 1 wt% to 70 wt% copper compound, 1 wt% to 20 wt% bismuth compound, 0 wt% to 10 wt% binder, and the balance being naphthoic ore or EMD. In another embodiment, the cathode material is substantially composed of 2 wt% to 30 wt% conductive carbon, 0 wt% to 30 wt% conductive metal additives, 1 wt% to 20 wt% bismuth compound, 0 wt% to 10 wt% binder, and the balance being naphthoic ore or EMD.

[0044] The porosity of the cathode, determined by mercury intrusion porosimetry, ranges from 20% to 85%. Porosity can be measured according to the version of ASTM D4284-12, "Standard Test Method for Determination of Pore Volume Distribution of Catalysts and Catalyst Supports by Mercury Intrusion Porosimetry," as of the date of this application.

[0045] The cathode material 2 can be formed on the cathode current collector 1, which is 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), nickel-plated steel, nickel-plated copper, tin-plated steel, copper-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 be formed as a mesh (e.g., expanded mesh, woven mesh, etc.), perforated metal, foam, foil, felt, fibrous architecture, porous block structure, perforated foil, wire mesh, wrapped assembly, or any combination thereof. In some embodiments, the current collector can form a pocket assembly or form part of a pocket assembly, wherein the pocket can hold the cathode material 2 within the current collector 1. A connecting piece (e.g., a portion of the cathode current collector 1 extending to the outside of the cathode material 2, such as...) Figure 3B The top of the intermediate cathode 12 (shown) can be connected to a current collector to provide an electrical connection between the external power supply and the current collector.

[0046] The cathode material 2 can be pressed onto the cathode current collector 1 to form the cathode 12. For example, it can be between 1000 psi and 20000 psi (6.9 × 10⁻⁶). 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 Pascals). The cathode material 2 can be adhered to the cathode current collector 1 in the form of a paste. The resulting cathode 12 can have a thickness between about 0.1 mm and about 5 mm.

[0047] A variety of anode materials can be accommodated by using electrolytes with different properties as described herein. In some embodiments, the anode may include lithium, zinc, aluminum, magnesium, iron, calcium, strontium, lanthanum, potassium, sodium, zirconium, titanium, titanium oxide, indium, indium oxide, indium hydroxide, zinc oxide, Mn3O4, zinc manganese ore (ZnMn2O4), vanadium, tin, tin oxide, barium hydroxide, barium, cesium, aluminum hydroxide, copper, bismuth, silicon, carbon, and any mixture of these materials. The battery described herein can be formed by pairing any of the cathode materials and anode materials described herein, provided that the materials mentioned above generate voltage in the presence of a suitable electrolyte (e.g., a suitable anode electrolyte and cathode electrolyte, etc.).

[0048] 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 Zn anode mixture includes zinc, zinc oxide (ZnO), a conductive material, and a binder. In the anode material 5, Zn may be present in amounts from about 50 wt% to about 90 wt%, or from about 60 wt% to about 80 wt%, or from about 65 wt% to about 75 wt%, based on the total weight of the anode material. In addition to zinc, 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, and combinations thereof, wherein each element may be present in the same or similar amounts as zinc described herein.

[0049] 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. Those skilled in the art will understand, and with the aid of this disclosure, that the purpose of the ZnO in the anode mixture is to provide a Zn source during the recharging step, and that the zinc present may be converted between zinc and zinc oxide during the charging and discharging phases.

[0050] In one embodiment, optionally, the conductive material may 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 those skilled in the art will understand, and with the aid of this disclosure, the conductive material may be used as a conductive agent in the anode mixture, for example, to enhance the overall conductivity of the anode mixture. Non-limiting examples of suitable conductive materials may include any conductive carbon described herein, such as carbon, graphite, graphite powder, graphite flakes, graphite spheres, carbon black, activated carbon, conductive carbon, amorphous carbon, vitrified 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, graphynylene, or any combination thereof.

[0051] The anode material 5 may also contain a binder. Typically, the binder serves to hold the electroactive material particles together and bring them into contact with the current collector. The binder may be present at a concentration of 0 wt% to 10 wt%. The binder may include water-soluble cellulose-based hydrogels such as methylcellulose (MC), carboxymethylcellulose (CMC), hydroxypropylcellulose (HPH), hydroxypropyl methylcellulose (HPMC), hydroxyethyl methylcellulose (HEMC), carboxymethyl hydroxyethyl cellulose, and hydroxyethyl cellulose (HEC), which act as thickeners and strong binders and have been crosslinked with polymers such as polyvinyl alcohol, polyvinyl acetate, polyaniline, polyvinylpyrrolidone, polyvinylidene fluoride, and polypyrrole with good mechanical strength. The binder may also be a cellulose membrane sold in cellophane form. The binder may also be PTFE, a highly resistive material that 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.

[0052] In some embodiments, the anode material 5 can be used independently 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 be in the form or structure of foil, mesh, perforated layer, foam, felt, or powder. For example, the anode can include a metal foil electrode, a mesh electrode, or a perforated metal foil electrode.

[0053] In some embodiments, anode 13 may optionally include an anode current collector 4. Anode current collector 4 can be used with anode 13, including all those described relative to cathode 12. Anode material 5 can be pressed onto anode current collector 4 to form anode 13. For example, it can be between 1000 psi and 20000 psi (6.9 × 10⁻⁶). 6 and 1.4×10 8 The anode material 5 is adhered to the anode current collector 4 by pressing under pressure (between Pascals). The anode material 5 can be adhered to the anode current collector 4 in the form of a paste. When the anode current collector 4 has connecting tabs, it can extend outside the device to form current collector connecting tabs. The resulting anode 13 can have a thickness between about 0.1 mm and about 5 mm.

[0054] like Figure 3B As shown, battery 10 may not include a separator. The ability to form a separator-free battery 10 allows for a reduction in the overall cost of the battery while maintaining the same or similar performance as a battery with a separator. The use of PGE acts as a separator by forming a physical barrier between the anode 13 and the cathode 12 to prevent short circuits.

[0055] In such Figure 3A and Figure 3C In some embodiments shown, when the electrodes are constructed into a battery, a spacer 9 may be provided between the anode 13 and the cathode 12 (e.g., as shown in the figure). Figure 3C (as shown) and / or buffer layer 21 (e.g., as shown) Figure 3A (As shown). Although shown as being disposed between anode 13 and cathode 12, spacer 9 may be used to enclose one or more of anode 13 and / or cathode 12, or alternatively, to enclose one or more anode 13 and / or cathode 12 when there are multiple anodes 13 and cathodes 12.

[0056] The separator 9 may include one or more layers. For example, when using a separator, one to five layers of separator may be applied between adjacent electrodes. The separator may be formed of suitable materials such as nylon, polyester, polyethylene, polypropylene, poly(tetrafluoroethylene) (PTFE), poly(vinyl chloride) (PVC), polyvinyl alcohol, cellulose, or any combination thereof. Suitable layer and separator forms may include, but are not limited to, 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 with a contact angle with water of less than 45°. In another embodiment, the contact angle with water is less than 30°. In yet another embodiment, the contact angle with water is less than 20°. The polyolefin may be added, for example, by adding TRITON X-100. TM Alternatively, it can be modified by oxygen plasma treatment. In some embodiments, the separator 9 may include... The brand's microporous separator. In one embodiment, separator 9 may include an FS 2192 SG membrane, which may be a polyolefin nonwoven membrane sourced from Freudenberg, Germany. In some embodiments, the separator may include a lithium superion conductor. Sodium superionic conductor (NASION) Bipolar membranes, water electrolysis membranes, composites of polyvinyl alcohol and graphene oxide, polyvinyl alcohol, cross-linked polyvinyl alcohol, or combinations thereof.

[0057] While the separator 9 may comprise a variety of materials, using PGE as the electrolyte allows for the use of a relatively inexpensive separator 9 when one or more separators are present. For example, the separator 9 may comprise... Polyvinyl alcohol, Polyvinyl alcohol and graphene oxide composites, cross-linked polyvinyl alcohol, And / or a carbon-polyvinyl alcohol complex. Using separator 9 can help improve the cycle life of battery 20, but it is not necessary in all embodiments.

[0058] When using buffer layer 21, it can be used alone or in combination with separator 9. Buffer layer 21 may include a gel solution having the same electrolyte formulation as the anolyte and / or catholyte. For example, buffer layer 21 may be PGE as described herein. One or more additives may also be present in buffer layer 21, such as calcium hydroxide, layered double hydroxides (e.g., hydrotalcite), pentargyrite, titanate, magnesium hydroxide, or combinations thereof. For example, when the anolyte and catholyte have the same formulation but different compositions and / or viscosities, the buffer layer may have the same electrolyte concentration as the anolyte or catholyte, or a concentration between the anolyte and catholyte. The viscosity of the buffer layer may be greater than that of the anolyte or catholyte to help prevent mixing between the anolyte and catholyte and to limit ion migration between them.

[0059] like Figures 3A to 3D As shown, the cathode electrolyte 3 may contact the cathode 12, and the anode electrolyte 6 may contact the anode 13. As described in more detail herein, one or both of the cathode electrolyte 3 and / or the anode electrolyte 6 may polymerize or gel to form a separate gel electrolyte to prevent mixing between the two electrolyte solutions. The cathode electrolyte 3 may be disposed in the housing 7 in contact with the cathode material 2. In some embodiments, the anode electrolyte 6 may polymerize or gel, and the cathode electrolyte 3 may be liquid. Even if the cathode electrolyte 3 is liquid, polymerization of the anode electrolyte 6 can prevent mixing between the cathode electrolyte 3 and the anode electrolyte 6. In some embodiments, both the cathode electrolyte 3 and the anode electrolyte 6 are gelled.

[0060] The cathode electrolyte 3 can be an acidic or neutral solution, and the pH value of the cathode electrolyte can be between -1.2 and 7. The cathode electrolyte 3 can be used at temperatures between 0 and 200°C. In some embodiments, the cathode electrolyte may include an acid, such as a mineral acid (e.g., hydrochloric acid, nitric acid, sulfuric acid, etc.). For acidic cathode electrolyte compositions, the acid concentration can be between about 0 M and 16 M. In some embodiments, the cathode electrolyte solution may include: containing potassium permanganate, sodium permanganate, lithium permanganate, calcium permanganate, manganese sulfate, manganese chloride, manganese nitrate, manganese perchlorate, manganese acetate, bis(trifluoromethanesulfonic acid) manganese, 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, or sodium sulfate. Solutions of 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 any combination thereof. For example, the cathode electrolyte solution may include manganese sulfate mixed with sulfuric acid or potassium permanganate mixed with sulfuric acid. Other dopants in the solution may be zinc sulfate, lead sulfate, titanium disulfide, hydrated titanium sulfate, silver sulfate, cobalt sulfate, and nickel sulfate. In some embodiments, the cathode electrolyte solution may include salts of manganese sulfate, ammonium chloride, ammonium sulfate, manganese acetate, potassium permanganate, and / or permanganate, wherein the concentration of the additives may be between 0M and 10M. Depending on the type of manganese salt used, the voltage of the battery system may vary. For example, in manganese sulfate electrolyte, the voltage of SS-HiVAB is about 2.45-2.5V, while in potassium permanganate electrolyte, the voltage of SS-HiVAB is about 2.8-2.9V.

[0061] In some embodiments, the cathode electrolyte may include permanganate. Permanganate has a very high positive potential. This can increase the overall battery potential within the battery 10. When permanganate is present, it may be present in a molar ratio of acid (e.g., inorganic acid, such as hydrochloric acid, sulfuric acid, etc.) to permanganate between about 5:1 and about 1:5, or 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 depending on the intended operating conditions of the battery 10. The concentration of permanganate (e.g., potassium permanganate or permanganate, etc.) may be greater than 0 and less than or equal to 5 M. In some embodiments, the cathode electrolyte solution includes sulfuric acid, hydrochloric acid, or nitric acid with a concentration greater than 0 and less than or equal to 16 M. The use of permanganate is advantageous for manufacturing high-voltage batteries, such that when a cathode electrolyte containing permanganate is used in conjunction with an extremely negative anode potential, the resulting battery voltage can be approximately 2.8 V when the cathode and anode are MnO2|Zn, and approximately 4 V when the cathode and anode are MnO2|Al. When the cathode electrolyte contains permanganate, suitable permanganate may include, but is not limited to, potassium permanganate, sodium permanganate, lithium permanganate, calcium permanganate, and combinations thereof.

[0062] In some embodiments, the anolyte can be an alkaline electrolyte, while the cathode electrolyte can be an acidic or neutral solution. The alkaline electrolyte in the anolyte can be a hydroxide, such as potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonia hydroxide, cesium hydroxide, or any combination thereof. The resulting anolyte may have a pH greater than 7. In some embodiments, the pH of the anolyte may be greater than or equal to 10 and less than or equal to about 15.13. As described herein, the anolyte can be polymerized or gelled. The resulting anolyte may be semi-solid and non-flowing within the battery. This can be used to limit or prevent any mixing between the anolyte and the cathode electrolyte. The anolyte can be polymerized using any suitable technique, including any techniques described herein. Higher concentrations of alkaline electrolytes are typically used to increase the solubility of any metal in the gel state. For example, higher concentrations of the anolyte can range from 25 wt% to 70 wt%.

[0063] In addition to hydroxides, the anolyte 6 may also include additional components. In some embodiments, the alkaline electrolyte may have zinc oxide, potassium carbonate, potassium iodide, and potassium fluoride as additives. When a zinc compound is present in the anolyte, the anolyte 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 combinations thereof.

[0064] In some embodiments, an organic solvent containing a suitable salt can be used as the electrolyte. Examples of suitable organic solvents include, but are not limited to, cyclic carbonates, linear carbonates, dialkyl carbonates, aliphatic carboxylic acid esters, γ-lactones, linear ethers, cyclic ethers, aprotic organic solvents, fluorinated carboxylic acid esters, and combinations thereof. Any suitable additive, including the salts described herein, can be used with the organic solvent to form an organic electrolyte for anolyte and / or catholyte.

[0065] In some embodiments, ionic liquids can be used to form gel electrolytes (e.g., gel anolytes, gel cathode electrolytes, etc.). Ionic liquids may include 1-ethyl-3-methylimidazolium chloride (EMImCl), 1-allyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium chloride, 1-ethyl-3-methylacetic acid imidazolium, 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methyltetrachloroaluminate imidazolium, lithium hexafluorophosphate (LiPF6), lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(oxalate)borate, and combinations thereof. Other ionic liquids are known and may also be used. In some embodiments, EMImCl can be used as the ionic liquid and can be purified before being mixed with an aluminum salt to form an aluminum-ion-conducting electrolyte. The aluminum salt may be aluminum chloride, aluminum acetate, aluminum nitrate, aluminum bromide, and others. A mixture of EMImCl and aluminum chloride can be prepared by slowly adding a precise amount of aluminum chloride in an inert atmosphere. The mixing ratio of aluminum chloride to EMImCl can be between 5:1 and 1:1, or about 1.5:1.

[0066] In some embodiments, water-in-salt electrolytes can be gelled and used as cathode and / or anodic electrolytes. Water-in-salt electrolytes may include electrolytes in which the salt concentration is above the saturation point. Increasing the salt concentration above the saturation point to form a water-in-salt electrolyte can further reduce the activity of water in an aqueous electrolyte. The ionic conductivity of such electrolytes can be higher than that of conventional aqueous electrolytes. Water-in-salt electrolytes may include water and a suitable salt above their saturation point, including any salts and additives described herein with respect to aqueous anodic and / or cathode electrolytes.

[0067] In some embodiments, the compounds in the anolyte and catholyte may be the same, but their concentrations may vary between the anolyte and catholyte. In these embodiments, the catholyte and anolyte may include any of the compounds listed above for describing the anolyte and / or catholyte. For example, the anolyte and catholyte may include hydroxides, such as potassium hydroxide. The concentration of hydroxide in contact with the anolyte may be higher than the concentration of hydroxide in the catholyte. Upon gelation, the viscosities of the anolyte and catholyte may differ. In some embodiments, the viscosity of the catholyte may be higher (e.g., resulting in a thicker gel). The viscosity of the anolyte...

[0068] One or both of the anolyte and cathode electrolyte can be gelled in the battery. The polymerization process can be carried out using any electrolyte, including any electrolyte described herein (e.g., organic electrolytes, aqueous electrolytes, ionic liquid electrolytes, high-salt electrolytes, etc.). Many polymerization techniques can be used to form gel / solid electrolytes, such as stepwise growth, chain growth, emulsion polymerization, solution polymerization, suspension polymerization, precipitation polymerization, photopolymerization, and others. Once the gel / solid electrolyte is formed through the polymerization step, they can be assembled in a single battery casing as described herein. The battery can use a separator, or it can be membrane-free or separator-free.

[0069] As described herein, electrolytes can be polymerized or gelled to form polymeric gel electrolytes (PGEs) for use as cathode and / or anodic electrolytes. The resulting PGE can be semi-solid and cannot flow within the battery. For example, a PGE can comprise an inert hydrophilic polymer matrix impregnated with an aqueous electrolyte. The electrolyte can be polymerized using any suitable technique. In embodiments, the method of forming a PGE can begin by selecting monomeric materials for the PGE. The monomer can be a polar vinyl monomer selected from the group consisting of acrylic acid, vinyl acetate, acrylates, vinyl isocyanate, acrylonitrile, or any combination thereof. An aqueous electrolyte component can then be selected and may include any of the components described above for the electrolyte. An initiator can be added to initiate the polymerization process. In some embodiments, a crosslinking agent can be used in the electrolyte composition to further crosslink the polymer matrix to form the PGE. The monomer (e.g., a polar vinyl monomer) in the composition can be present in an amount of about 5 wt% to about 50 wt%, the initiator can be present in an amount of about 0.001 wt% to about 0.1 wt%, and the crosslinking agent can be present in an amount of 0 to 5 wt%.

[0070] In some embodiments, PGE can be formed in situ, which refers to adding the electrolyte in liquid form to the housing, followed by a subsequent polymerization reaction to form PGE within the housing. This method allows the electrolyte composition to permeate into the void spaces, anode, and / or cathode to form PGE before complete polymerization. In some embodiments, a vacuum (e.g., a pressure less than atmospheric pressure) can be created within the housing 7 when the electrolyte is introduced into the respective compartment. The vacuum can be used to remove air and allow the electrolyte to permeate the various void spaces within the anode 13, cathode 12, and / or battery 10. In some embodiments, the vacuum can be between about 10 and 29.9 inches of mercury or between about 20 and about 29.9 inches of mercury. Using a vacuum helps to avoid the presence of air bubbles within the battery 10 before the electrolyte has fully polymerized. In some embodiments, the electrodes can be immersed in an electrolyte solution at a temperature of 0°C to 30°C for 1 to 120 minutes before the electrolyte has fully polymerized, so that the electrodes are electrolyte-impregnated. Once the electrolyte has polymerized, the battery can be left to stand before use. In some embodiments, the battery can be left to stand for 5 minutes to 24 hours.

[0071] To facilitate electrolyte impregnation of the electrodes, they can be pre-impregnated with a selected electrolyte solution prior to electrolyte polymerization. This can be done by immersing the electrodes in an electrolyte (e.g., in a cathode electrolyte or an anode electrolyte, respectively) outside the battery or housing, and then placing the pre-impregnated electrodes in the housing to construct the battery. In some embodiments, an electrolyte without polymers or gelling agents can be added to the battery to impregnate the electrodes in situ. This can include using a vacuum to assist the impregnation of the electrodes. The electrodes can be impregnated for approximately 1 minute to 24 hours. In some embodiments, the impregnation can be performed in multiple cycles, wherein the battery is filled with electrolyte and impregnated, drained, refilled and impregnated, and then drained for the required number of cycles. While the electrodes are being impregnated and impregnated with the electrolyte, the electrolyte containing polymers and polymerization agents (e.g., initiators, crosslinking agents, etc.) can be added to the housing and polymerized to form the final battery.

[0072] The composition of the electrolyte, monomer materials, initiator, and formation conditions (e.g., temperature) can be selected to provide the desired polymerization time, allowing the electrolyte composition to properly immerse the battery components for absorption and permeation into the electrodes. The polymerization process can be controlled by temperature; lower temperatures can inhibit or slow down the polymerization reaction, while higher temperatures can reduce polymerization time or accelerate the process. Furthermore, increasing the alkaline electrolyte component (such as hydroxide) can reduce polymerization time, and increasing the initiator concentration also reduces polymerization time. Depending on the composition of the electrolyte solution and the reaction temperature, suitable polymerization times can range from 1 minute to 24 hours.

[0073] As an example of a polymerization method, a mixture of acrylic acid, N,N'-methylenebisacrylamide, and an alkaline solution can be produced at approximately 0°C. Any additives (e.g., gas suppressants, additional additives as described herein, etc.) can then be added to the solution. For example, when zinc oxide is used in the electrolyte, it can be dissolved in an alkaline solution after mixing the precursor components, where zinc oxide is beneficial in the electrochemical cycle at the anode. To polymerize the resulting mixture, an initiator such as potassium persulfate can be added to initiate the polymerization process and form a solid or semi-solid polymeric electrolyte (e.g., PGE). Once the polymerization process has occurred, the resulting polymeric electrolyte is stable over time.

[0074] For example, the PGE described herein can be prepared by free radical polymerization. In one embodiment, acrylic acid (AA) can be used as a monomer, N,N'-methylenebisacrylamide (MBA) as a crosslinking agent, and potassium persulfate (K₂S₂O₈) as an initiator. An alkaline electrolyte, such as KOH, can be added to this process and can be embedded into the backbone. The addition of an alkaline electrolyte to AA results in neutralization, which reduces the concentration of the alkaline electrolyte in the polymer gel. Figure 4Theoretical and experimental values ​​for AA neutralization in KOH are reported. The purpose of this figure is to serve as a guide for appropriate PGE concentrations for various electrode combinations. Similarly, different alkaline electrolyte concentrations can alter gelation time. Higher alkaline electrolyte concentrations generally result in faster gelation, while lower concentrations require longer times. Initiator concentration can also affect the gelation process. Figure 5 The report provides an in-depth analysis of this process, which is again used as a guide for the preparation of PGE. The viscosity of the gel can be adjusted by changing the monomer and MBA concentrations, thereby affecting the ionic conductivity.

[0075] The polymerization process can occur before or after the construction of battery 10. In some embodiments, the electrolyte can be polymerized and placed in a tank to form a sheet. Once polymerized, the sheet can be cut to a suitable size and shape, and one or more layers can be used to form the electrolyte 15 in contact with the anode 13. When using a pre-formed PGE, additional liquid electrolyte can be introduced into the battery, and / or the electrodes can be pre-soaked in the electrolyte before the battery is constructed.

[0076] In some embodiments, aqueous electrolytes, organic electrolytes, ionic liquids, high-salt electrolytes, etc., can be used to form the PGE. In some embodiments, the aqueous electrolyte can be used as the cathode electrolyte and / or anode electrolyte and gelled to form an aqueous hydrogel as the PGE. In some embodiments, the aqueous hydrogel can be prepared by free radical polymerization. For example, acrylic acid (AA) can be selected as the monomer, N,N'-methylenebisacrylamide (MBA) as the crosslinking agent, and potassium persulfate as the initiator. In aqueous alkaline batteries, suitable hydroxides (e.g., potassium hydroxide (KOH), sodium hydroxide, lithium hydroxide, etc.) can be used to form the electrolyte. By neutralizing the hydroxide with AA, the hydroxide can be encapsulated in the hydrogel network. To generate the hydrogel, the monomer can be combined with any crosslinking agent until the crosslinking agent dissolves. Additionally, a certain amount of hydroxide can be cooled to slow down the reaction. In some embodiments, where the electrolyte is an aqueous electrolyte, the hydroxide can be cooled to temperatures below about 10°C, below about 5°C, or below about 0°C. Because the neutralization reaction is exothermic, a mixture of monomer and any crosslinking agent can be added dropwise to a cooled hydroxide solution. To gel the resulting mixture of hydroxide, monomer, and crosslinking agent, an initiator, such as potassium persulfate, can be added. The mixture is then allowed to form PGE. The amount and concentration of the components can be varied to obtain hydrogels with different mechanical strengths.

[0077] Electrolytes, including ionic liquids, can also be used to form PGEs, including any ionic liquids described herein. To form a PGE using an ionic liquid, a solution of any additive (which may be in a suitable solvent) can be prepared, and a monomer can be added. This monomer can be any suitable monomer. For example, acrylamide can be used as a polymerization agent for the ionic liquid. For this solution, the ionic liquid and additive solution can be mixed with an initiator. Any suitable initiator used with the polymerization agent can be used. For example, azobisisobutyronitrile (AIBN) can be used with acrylamide. The initiator can be added in a suitable amount, for example, about 1 wt% of the polymerization agent. The final solution is then heated to form a polymer gel.

[0078] Organic electrolytes containing salts dissolved in organic solvents can also be gelled to form anolytes and / or catholytes. For example, lithium-ion conductive electrolytes can be gelled using a variety of polymerization techniques, such as ring-opening polymerization, photo-initiated free radical polymerization, UV-initiated free radical polymerization, thermally initiated polymerization, in-situ polymerization, UV irradiation, electrospinning, and other techniques. Lithium electrolytes can include lithium hexafluorophosphate (LiPF6), lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(oxalate)borate, and combinations thereof in organic solvents such as ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate, methyl ethyl carbonate, and combinations thereof. An exemplary mixture may include 1M LiPF6 mixed in a solvent mixture of ethylene carbonate and dimethyl carbonate. Other solvents are also available that can be used as mixtures to reduce the flammability of the organic electrolyte.

[0079] Organic electrolytes can be gelled by mixing a selected salt with an organic solvent. A gelling agent and an initiator can then be added. The gelling agent can be added in an amount from about 0.1 wt% to about 5 wt% of the mixture, and the initiator can be added in an amount from about 0.01 wt% to about 1 wt% of the mixture. In some embodiments, a suitable gelling agent for the organic electrolyte may include pentaerythritol tetraacrylate, and the initiator may include azobisisobutyronitrile (AIBN). The resulting mixture can be gelled (e.g., polymerized) by heating it to about 50-90°C, or heating it to about 70°C and holding it for 1-24 hours.

[0080] For acidic or neutral aqueous electrolytes, polymerization can be carried out by various methods. In one embodiment, a method for preparing a solid-gelled aqueous acidic or neutral electrolyte may include adding acrylamide to a solution containing manganese sulfate, H₂SO₄, ammonium sulfate, potassium permanganate, and / or sulfuric acid. A gelling agent containing acrylamide may be added to the solution and mixed at a temperature of about 70-90°C for at least one hour until the solution is homogenized. After the solution is homogenized, a crosslinking agent and an initiator may be added to the solution and mixed for 2-48 hours until the solution gels.

[0081] The final battery or battery design will have a cathode with a lower PGE alkaline concentration and an anode with a higher PGE alkaline concentration, and will have a separator or buffer layer to prevent the two PGEs from mixing. This final battery with dual electrolytes allows for high reversibility and improved or maximized utilization of the electrodes, resulting in higher energy density.

[0082] Example

[0083] The implementation methods have been generally described. The following embodiments are given in the form of specific implementations of this application and are used to demonstrate the practice and advantages of this application. It is understood that the embodiments are given by way of illustration and are not intended to limit the specification or claims in any way.

[0084] Example 1

[0085] The performance of the MnO2 cathode was tested in an aqueous solution with a low KOH concentration of 10 wt%. The cathode consisted of 80 wt% MnO2 (EMD), 15 wt% graphite, and 5 wt% Teflon, pressed onto a nickel current collector. The counter electrode used in the experiment was sintered nickel. Zn was avoided as the anode in this experiment to eliminate any adverse effects of Zn on the performance of MnO2 in aqueous KOH. Cellophane was used as a separator. The cell potential was monitored on a mercury / mercury oxide (Hg / HgO) reference electrode. The cathode was cyclicated at 40% utilization of the theoretical single-electron capacity (308 mAh / g).

[0086] The battery's performance is as follows: Figure 6 As shown. Due to the low solubility of Mn ions, the battery can cycle stably at low KOH concentrations. The battery shows no capacity decay in each charge-discharge cycle. If the battery potential relative to Hg|HgO reaches -0.4V, this would indicate a capacity decay loss; however, as... Figure 6 As shown, the cathode can release its capacity of ~150mV under voltage limitations. -0.4V relative to Hg|HgO corresponds to ~1V relative to the Zn anode, which will be the endpoint of the actual cell's discharge potential. However, similar cells with KOH concentrations >25wt% will experience faster capacity decay due to the high solubility of Mn ions.

[0087] Example 2

[0088] The cycling performance of the Zn mesh anode in high-concentration PGE was tested. The PGE was prepared from 45 wt% KOH, of which approximately 30 wt% remained after the gelation process. Figure 4As shown. A Zn mesh purchased from a commercial supplier was tested in a cell using an oversized Zn anode as the counter electrode. This oversized zinc anode also served as a reference in the cell. Cellophane was used as a separator. The cycling performance of the Zn mesh in high-concentration PGE is shown in... Figure 7 As shown in the figure, it can be seen that the Zn network has very stable performance in the gelled network.

[0089] Example 3

[0090] The full-discharge performance of a complete MnO2|Zn battery was tested under a dual-electrolyte design. The cathode consisted of 80 wt% MnO2 (EMD), 15 wt% graphite, and 5 wt% Teflon, pressed onto a nickel current collector. The MnO2 cathode was coated with PGE made from a low KOH concentration (20 wt%), while the Zn mesh anode was coated with PGE made from a high KOH concentration (50 wt%). Polyvinyl alcohol (PVA) was used as the separator. The battery was cycled to obtain maximum discharge performance. Performance was as follows: Figure 8 As shown, it can be seen that the dual-electrolyte battery can release 1e of capacity at the end of discharge.

[0091] Example 4

[0092] The cycleability of a complete MnO2|Zn battery was tested under a dual-electrolyte design. The cathode consisted of 80 wt% MnO2 (EMD), 15 wt% graphite, and 5 wt% Teflon, pressed onto a nickel current collector. The anode consisted of 95 wt% Zn powder (doped with bismuth and indium) and 5 wt% Teflon. The MnO2 cathode was coated with PGE made from a low KOH concentration (25 wt%), while the Zn mesh anode was coated with PGE made from a high KOH concentration (45 wt%). Polyvinyl alcohol (PVA) was used as the separator. The cycle performance of the battery was as follows: Figure 9 As shown, it is designed to release 40% of the single-electron capacity of MnO2. Performance-wise, the battery can cycle stably and release its designed capacity before the battery voltage (1V) ends.

[0093] Example 5

[0094] The cycleability of a complete MnO2|Zn battery was tested under a dual-electrolyte design, where the cathode PGE has expanded carbon embedded within its framework to enhance MnO2 performance. The cathode consists of 80 wt% MnO2 (EMD), 15 wt% graphite, and 5 wt% Teflon, pressed onto a nickel current collector. The anode is composed of a Zn mesh. The MnO2 cathode is covered with PGE made from a low KOH concentration (25 wt%), which has expanded graphite (BNB-90) embedded within its framework during gelation, while the Zn mesh anode is covered with PGE made from a high KOH concentration (54 wt%). Polyvinyl alcohol (PVA) is used as the separator. The cycle performance of the battery is as follows: Figure 10 As shown, it is designed to release 40% of the single-electron capacity of MnO2. Performance-wise, the battery is able to cycle stably and release its designed capacity before the battery voltage (1V) ends. Expanded graphite is contained in the framework as a source to capture dissolved Mn ions (if present). Graphite acts as a conductive framework in the PGE, allowing Mn to be deposited if it dissolves from the local electrode framework. Under the influence of charge, the deposited Mn can be converted back to its 4+ valence state.

[0095] Example 6

[0096] The cycleability of a complete MnO2|Zn battery was tested under a dual-electrolyte design, where the cathode was densified. The cathode consisted of 80 wt% MnO2 (EMD), 15 wt% graphite, and 5 wt% Teflon, pressed onto a nickel current collector. The anode consisted of a Zn mesh. The MnO2 cathode was coated with PGE made from a low KOH concentration (20 wt%), while the Zn mesh anode was coated with PGE made from a high KOH concentration (50 wt%). Polyvinyl alcohol (PVA) was used as the separator. The cycle performance of the battery was as follows: Figure 11 As shown, it was designed to release 40% of the single-electron capacity of MnO2. Performance-wise, the battery is able to cycle stably and release its designed capacity before the battery voltage (1V) ends. The densified cathode and low PGE concentration contribute to improved battery voltage behavior.

[0097] This document has described various batteries, systems, and methods, and specific aspects may include, but are not limited to:

[0098] In a first aspect, a dual-electrolyte battery includes: a cathode; an anode; a cathode electrolyte in contact with the cathode, wherein the cathode electrolyte comprises a first gel electrolyte solution; and an anode electrolyte in contact with the anode, wherein the anode electrolyte comprises a second gel electrolyte solution; wherein the electrolyte concentration in the anode electrolyte is higher than the electrolyte concentration in the cathode electrolyte.

[0099] The second aspect may include the battery of the first aspect, which further includes: a separator disposed between the anode electrolyte and the cathode electrolyte.

[0100] The third aspect may include the battery of the first aspect, further comprising: a buffer layer disposed between the anode electrolyte and the cathode electrolyte, wherein the buffer layer comprises a third gel electrolyte solution.

[0101] The fourth aspect may include a battery of any one of the first to third aspects, wherein the viscosity of the first gel electrolyte solution is higher than the viscosity of the second gel electrolyte solution.

[0102] The fifth aspect may include a battery according to any one of the first to fourth aspects, wherein the cathode comprises an active material, and wherein the active material comprises at least one of the following: manganese oxide; lithium manganese oxide; aluminum manganese oxide; zinc manganese oxide; copper manganese oxide; bismuth manganese oxide; copper intercalated naphthoic ore; copper intercalated bismuth naphthoic ore; tin-doped manganese oxide; magnesium manganese oxide; silver oxide; silver dioxide; silver; nickel hydroxyl oxide; nickel hydroxide; nickel; lead oxide; copper oxide; copper dioxide; lead; lead dioxide; potassium persulfate; sodium persulfate; ammonium persulfate; potassium permanganate; calcium permanganate; barium permanganate; silver permanganate; ammonium permanganate; peroxide; gold ; perchlorate; cobalt oxide; lithium cobalt oxide; sodium cobalt oxide; perchlorate; nickel oxide; bromine; mercury; vanadium oxide; bismuth vanadium oxide; hydroquinone; calix[4] quinone; tetrachlorobenzoquinone; 1,4-naphthoquinone; 9,10-anthraquinone; 1,2-naphthoquinone; 9,10-phenanthroquinone; nitrogen oxide-ammonium oxide cation redox pairs, such as (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO); carbon; 2,3-dicyano-5,6-dichlorodicyanoquinone; tetracyanoethylene; sulfur trioxide; ozone; oxygen; air; lithium nickel manganese cobalt oxide; sulfur; lithium iron phosphate; lithium copper oxide; lithium copper oxyphosphate; and any mixture thereof.

[0103] The sixth aspect may include a battery of any one of the first to fifth aspects, wherein the cathode comprises conductive carbon, and wherein the conductive carbon comprises graphite, carbon fiber, carbon black, acetylene black, single-walled carbon nanotubes, multi-walled carbon nanotubes, nickel or copper coated carbon nanotubes, dispersions of single-walled carbon nanotubes, dispersions of multi-walled carbon nanotubes, graphene, graphyne, graphene oxide, and combinations thereof.

[0104] The seventh aspect may include a battery of any one of the first to sixth aspects, wherein the cathode includes an adhesive, and wherein the adhesive includes polytetrafluoroethylene, carboxymethyl cellulose, polyvinyl alcohol, or a combination thereof.

[0105] The eighth aspect may include a battery of any one of the first to seventh aspects, wherein the cathode comprises 1 wt% to 95 wt% of active material, 4 wt% to 98 wt% of conductive carbon, and 1 wt% to 5 wt% of binder.

[0106] The ninth aspect may include a battery of any one of the first to eighth aspects, wherein the cathode includes a pressed cathode material on a current collector, wherein the current collector includes carbon, lead, zinc, stainless steel, copper, nickel, silver, bismuth, titanium, magnesium, aluminum, indium, tin, gold, polypropylene, or a combination thereof.

[0107] The tenth aspect may include the battery of the ninth aspect, wherein the current collector is a mesh, foil, foam, felt, fiber, porous block structure, or a combination thereof.

[0108] The eleventh aspect may include a battery of any one of the first to tenth aspects, wherein the anode comprises an anode active material, and wherein the anode active material comprises zinc, aluminum, iron, copper, bismuth, tin, lithium, magnesium, calcium, titanium, or combinations thereof.

[0109] The twelfth aspect may include a battery of any one of the first to eleventh aspects, wherein the anode comprises 90% to 100% active material and 0% to 10% binder.

[0110] The thirteenth aspect may include a battery of any one of the first to twelfth aspects, wherein the anode includes an adhesive, and wherein the adhesive includes polytetrafluoroethylene, carboxymethyl cellulose, polyvinyl alcohol, or a combination thereof.

[0111] The fourteenth aspect may include a battery of any one of the first to thirteenth aspects, wherein the first gel electrolyte solution comprises an alkaline solution embedded in the gel, and wherein the concentration of the alkaline solution ranges from 1 wt% to 25 wt%.

[0112] The fifteenth aspect may include a battery of any one of the first to fourteenth aspects, wherein the second gel electrolyte solution comprises an alkaline solution embedded in the gel, and wherein the concentration of the alkaline solution ranges from 20 wt% to 55 wt%.

[0113] The sixteenth aspect may include a battery of any one of the first to fifteenth aspects, wherein the alkaline solution comprises potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, or a combination thereof.

[0114] The seventeenth aspect may include a battery of any one of the first to sixteenth aspects, wherein the anode electrolyte, the cathode electrolyte, or both include one or more electrolyte additives, wherein the electrolyte additives include expanded graphite, carbon nanotubes, carbon black, graphene oxide, graphene, potassium carbonate, potassium fluoride, barium hydroxide, polytetrafluoroethylene, indium hydroxide, bismuth oxide, titanium oxide, cellulose fibers, or combinations thereof.

[0115] The eighteenth aspect may include a battery of any one of the first to seventeenth aspects, further comprising: at least one of a separator or buffer layer disposed between the anode electrolyte and the cathode electrolyte, wherein at least one of the separator or buffer layer comprises cellophane, Celgard, polyvinyl alcohol, cross-linked polyvinyl alcohol, calcium hydroxide, polymer gel electrolyte, layered double hydroxide, NASICON, LISICON, or a combination thereof.

[0116] In a nineteenth aspect, a dual-electrolyte battery includes: a cathode; an anode; a cathode electrolyte in contact with the cathode, wherein the cathode electrolyte comprises a first gel electrolyte solution; and an anode electrolyte in contact with the anode, wherein the anode electrolyte comprises a second gel electrolyte solution; wherein the first gel electrolyte solution and the second gel electrolyte solution comprise hydroxides, and wherein the concentration of hydroxides in the anode electrolyte is higher than the concentration of hydroxides in the cathode electrolyte.

[0117] The twentieth aspect may include the battery of the nineteenth aspect, further comprising: a separator disposed between the anode electrolyte and the cathode electrolyte.

[0118] The 21st aspect may include the battery of the 19th or 20th aspect, further comprising: a buffer layer disposed between the anode electrolyte and the cathode electrolyte, wherein the buffer layer comprises a third gel electrolyte solution.

[0119] The 22nd aspect may include a battery of any one of aspects 19 to 21, wherein the viscosity of the first gel electrolyte solution is higher than the viscosity of the second gel electrolyte solution.

[0120] The 23rd aspect may include the battery of any one of the 19th to 22nd aspects, wherein the concentration of hydroxide in the first gel electrolyte solution ranges from 1 wt% to 5 wt%.

[0121] The 24th aspect may include the battery of any one of aspects 19 to 23, wherein the concentration of hydroxide in the second gel electrolyte solution ranges from 20 wt% to 55 wt%.

[0122] The twenty-fifth aspect may include the battery of any one of aspects nineteen to twenty-four, wherein the hydroxide includes potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, or a combination thereof.

[0123] In a twenty-sixth aspect, a method of forming a dual-electrolyte battery includes: providing a cathode electrolyte in contact with a cathode, wherein the cathode electrolyte comprises a first gel electrolyte solution; providing an anode electrolyte in contact with an anode, wherein the anode electrolyte comprises a second gel electrolyte solution, wherein the hydroxide concentration in the anode electrolyte is higher than the hydroxide concentration in the cathode electrolyte; and providing at least one of a separator or a buffer layer between the anode electrolyte and the cathode electrolyte.

[0124] The twenty-seventh aspect may include the method of the twenty-sixth aspect, further comprising arranging the cathode electrolyte, the anode electrolyte, the anode and the cathode in a housing to form a battery.

[0125] The 28th aspect may include the method of the 26th or 27th aspect, wherein the buffer layer comprises a third gel electrolyte solution.

[0126] The 29th aspect may include the method of any one of aspects 26 to 28, wherein the viscosity of the first gel electrolyte solution is higher than the viscosity of the second gel electrolyte solution.

[0127] The thirtieth aspect may include the method of any one of the twenty-six to twenty-nine aspects, wherein the concentration of hydroxide in the first gel electrolyte solution ranges from 1 wt% to 25 wt%.

[0128] The 31st aspect may include the method of any one of aspects 26 to 30, wherein the concentration of hydroxide in the second gel electrolyte solution ranges from 20 wt% to 55 wt%.

[0129] The thirty-second aspect may include the method of any one of aspects twenty-six to thirty-one, wherein the hydroxide includes potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, or a combination thereof.

[0130] Embodiments are discussed herein with reference to the accompanying drawings. However, it will be readily understood by those skilled in the art that the detailed descriptions of these drawings given herein are for illustrative purposes, and the systems and methods extend beyond these limited embodiments. For example, it should be understood that, in light of the teachings of this specification, those skilled in the art will recognize numerous alternative and suitable methods for implementing the functionality of any given detail described herein, in addition to the specific implementation choices in the embodiments described and illustrated below, depending on the needs of a particular application. That is, numerous modifications and variations exist, too many to list, but all are within the scope of this specification. Furthermore, where appropriate, singular forms should be understood as plural and vice versa, masculine words should be understood as feminine words and vice versa, and alternative embodiments do not necessarily imply that they are mutually exclusive.

[0131] 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 subject to change. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the system and methods. It must be noted that, as used herein and in the appended claims (in this application or any derivative application thereof), the singular forms “a,” “an,” and “the” include plural references unless the context explicitly requires otherwise. Thus, 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 possible sense; therefore, unless the context explicitly requires otherwise, the word “or” should be understood as having the definition of logical “or” rather than logical “exclusive or.” The structures described herein should also be understood to refer to functional equivalents of such structures. Unless the context explicitly requires otherwise, language constituting the expression “approximate” should also be understood in this way.

[0132] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this specification pertains. While any methods, techniques, apparatuses, or materials similar to or equivalent to those described herein may be used in the practice or testing of this system and method, preferred methods, techniques, apparatuses, and materials are described. The structures described herein should also be understood to refer to functional equivalents of such structures. The system and method will now be described in detail with reference to the embodiments shown in the accompanying drawings.

[0133] Other variations and modifications will be apparent to those skilled in the art upon reading this application. Such variations and modifications may involve equivalents and other features known in the art that can be used to replace or supplement the features described herein.

[0134] Although the claims may constitute a particular combination of features in this application or any other application derived therefrom, it should be understood that the scope of this application also includes any novel feature or any novel combination of features or any generalization thereof explicitly or implicitly disclosed herein, 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 technical problems of the same kind as the system and method herein.

[0135] 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 sub-combination. It is hereby clarified by the applicant that new claims may be made for these features and / or combinations thereof during the course of this application or any further application derived therefrom.

Claims

1. A dual-electrolyte battery, comprising: Cathode, the cathode comprising MnO2; Anode, the anode comprising Zn; A cathode electrolyte in contact with the cathode, wherein the cathode electrolyte comprises a first gel electrolyte solution comprising a hydroxide; and The anolyte in contact with the anode, wherein the anolyte comprises a second gel electrolyte solution, the second gel electrolyte solution comprising the hydroxide, wherein the second gel electrolyte solution is a non-flowing semi-solid, wherein the hydroxide in the first gel electrolyte solution and the hydroxide in the second gel electrolyte solution are the same, and wherein the concentration of hydroxide in the anolyte is higher than the concentration of hydroxide in the cathode electrolyte. The viscosity of the first gel electrolyte solution is higher than that of the second gel electrolyte solution.

2. The dual-electrolyte battery according to claim 1, further comprising: An isolator is disposed between the anode electrolyte and the cathode electrolyte.

3. The dual-electrolyte battery according to claim 1, further comprising: A buffer layer is disposed between the anolyte and the cathode electrolyte, wherein the buffer layer comprises a third gel electrolyte solution.

4. The dual-electrolyte battery according to claim 1, wherein, The cathode further includes other cathode materials, wherein the other cathode materials include at least one of the following: lithium manganese oxide; aluminum manganese oxide; zinc manganese oxide; copper manganese oxide; bismuth manganese oxide; copper-intercalated naphthoic ore; copper-intercalated bismuth naphthoic ore; tin-doped manganese oxide; magnesium manganese oxide; silver oxide; silver dioxide; silver; nickel hydroxyl oxide; nickel hydroxide; nickel; lead oxide; copper oxide; copper dioxide; lead; lead dioxide; potassium persulfate; sodium persulfate; ammonium persulfate; potassium permanganate; calcium permanganate; barium permanganate; Silver permanganate; ammonium permanganate; gold; perchlorate; cobalt oxide; lithium cobalt oxide; sodium cobalt oxide; nickel oxide; vanadium oxide; bismuth vanadium oxide; hydroquinone; calix[4]quinone; tetrachlorobenzoquinone; 1,4-naphthoquinone; 9,10-anthraquinone; 1,2-naphthoquinone; 9,10-phenanthroquinone; (2,2,6,6-tetramethylpiperidin-1-yl)oxy; carbon; 2,3-dicyano-5,6-dichlorodicyanoquinone; tetracyanoethylene; lithium nickel manganese cobalt oxide; sulfur; lithium iron phosphate; lithium copper oxide; or lithium copper oxyphosphate.

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

6. The dual-electrolyte battery according to claim 5, wherein, The conductive carbon includes acetylene black.

7. The dual-electrolyte battery according to claim 1, wherein, The cathode further includes an adhesive, wherein the adhesive comprises polytetrafluoroethylene, carboxymethyl cellulose, polyvinyl alcohol, or a combination thereof.

8. The dual-electrolyte battery according to claim 1, wherein, The cathode comprises 1 wt% to 95 wt% of active material, 4 wt% to 98 wt% of conductive carbon, and 1 wt% to 5 wt% of binder.

9. The dual-electrolyte battery according to claim 1, wherein, The cathode includes a pressed cathode material on a current collector, wherein the current collector comprises carbon, lead, zinc, stainless steel, copper, nickel, silver, bismuth, titanium, magnesium, aluminum, indium, tin, gold, or combinations thereof.

10. The dual-electrolyte battery according to claim 9, wherein, The current collector is a mesh, foil, foam, or a combination thereof.

11. The dual-electrolyte battery according to claim 1, wherein, The anode further includes other anode active materials, wherein the other anode active materials include aluminum, iron, copper, bismuth, tin, lithium, magnesium, calcium, titanium, or combinations thereof.

12. The dual-electrolyte battery according to claim 1, wherein, The anode comprises 90% to 100% active material and 0% to 10% binder.

13. The dual-electrolyte battery according to claim 1, wherein, The anode includes an adhesive, wherein the adhesive includes polytetrafluoroethylene, carboxymethyl cellulose, polyvinyl alcohol, or a combination thereof.

14. The dual-electrolyte battery according to claim 1, wherein, The concentration of hydroxide in the first gel electrolyte solution ranges from 1 wt% to 25 wt%.

15. The dual-electrolyte battery according to claim 1, wherein, The concentration of hydroxide in the second gel electrolyte solution ranges from 20 wt% to 55 wt%.

16. The dual-electrolyte battery according to claim 1, wherein, The hydroxides include potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, or combinations thereof.

17. The dual-electrolyte battery according to claim 1, wherein, The anolyte, the catholyte, or both may include one or more electrolyte additives, wherein the electrolyte additives include expanded graphite, carbon nanotubes, carbon black, graphene oxide, graphene, potassium carbonate, potassium fluoride, barium hydroxide, polytetrafluoroethylene, indium hydroxide, bismuth oxide, titanium oxide, cellulose fibers, or combinations thereof.

18. The dual-electrolyte battery according to claim 1, further comprising: At least one of the separators or buffer layers disposed between the anode electrolyte and the cathode electrolyte, wherein at least one of the separators or buffer layers comprises cellophane, polyvinyl alcohol, cross-linked polyvinyl alcohol, calcium hydroxide, polymer gel electrolyte, layered double hydroxide, NASICON, LISICON, or a combination thereof.

19. A dual-electrolyte battery, comprising: MnO2 cathode; Zn anode; The cathode electrolyte in contact with the cathode, wherein the cathode electrolyte comprises a first gel-based alkaline electrolyte solution; and An anolyte in contact with the anode, wherein the anolyte comprises a second gel alkaline electrolyte solution, wherein the first gel alkaline electrolyte solution and the second gel alkaline electrolyte solution comprise hydroxides, wherein the hydroxides in the first gel alkaline electrolyte solution and the second gel alkaline electrolyte solution are the same, and wherein the hydroxide concentration in the anolyte is higher than the hydroxide concentration in the cathode electrolyte. The viscosity of the first gel alkaline electrolyte solution is higher than that of the second gel alkaline electrolyte solution.

20. The dual-electrolyte battery according to claim 19, further comprising: An isolator is disposed between the anode electrolyte and the cathode electrolyte.

21. The dual-electrolyte battery according to claim 19, further comprising: A buffer layer is disposed between the anolyte and the cathode electrolyte, wherein the buffer layer comprises a third gel alkaline electrolyte solution.

22. The dual-electrolyte battery according to claim 19, wherein, The concentration of hydroxide in the first gel alkaline electrolyte solution ranges from 1 wt% to 25 wt%.

23. The dual-electrolyte battery according to claim 19, wherein, The concentration of hydroxide in the second gel alkaline electrolyte solution ranges from 20 wt% to 55 wt%.

24. The dual-electrolyte battery according to claim 19, wherein, The hydroxides include potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, or combinations thereof.

25. A method for forming a dual-electrolyte battery, the method comprising: A cathode electrolyte is provided in contact with the cathode, the cathode comprising MnO2, wherein the cathode electrolyte comprises a first gel electrolyte solution comprising a hydroxide; An anolyte is provided in contact with the anode, the anode comprising Zn, wherein the anolyte comprises a second gel electrolyte solution, the second gel electrolyte solution comprising the hydroxide, wherein the hydroxide in the first gel electrolyte solution and the hydroxide in the second gel electrolyte solution are the same, and wherein the hydroxide concentration in the anolyte is higher than the hydroxide concentration in the cathode electrolyte; and At least one of a separator or a buffer layer is provided between the anode electrolyte and the cathode electrolyte; The viscosity of the first gel electrolyte solution is higher than that of the second gel electrolyte solution.

26. The method of claim 25, further comprising: The cathode electrolyte, the anode electrolyte, the anode, and the cathode are disposed in a housing to form a battery.

27. The method according to claim 25, wherein, The buffer layer includes a third gel electrolyte solution.

28. The method according to claim 25, wherein, The concentration of hydroxide in the first gel electrolyte solution ranges from 1 wt% to 25 wt%.

29. The method according to claim 25, wherein, The concentration of hydroxide in the second gel electrolyte solution ranges from 20 wt% to 55 wt%.

30. The method according to claim 25, wherein, The hydroxides include potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, or combinations thereof.

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