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High voltage batteries using gelled electrolyte — Research Foundation Of The City University Of New York (US12355061B2)

ABSTRACT

Abstract

A high voltage aqueous battery includes a cathode comprising a cathode electroactive material, an anode comprising an anode electroactive material, a catholyte solution in contact with the cathode, and a polymerized anolyte solution in contact with the anode. The catholyte solution can be polymerized, and an optional separator can be used between the anolyte and the catholyte.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a filing under 35 U.S.C. 371 as the National Stage of International Application No. PCT/US2020/039927, filed on Jun. 26, 2020 and entitled, “HIGH VOLTAGE BATTERIES USING GELLED ELECTROLYTE,” which claims priority to and claims the benefit of: 1) U.S. Provisional Application No. 62/867,959, filed on Jun. 28, 2019, and entitled “Membrane-Less High Voltage Aqueous Manganese Dioxide Battery,” 2) U.S. Provisional Application No. 62/877,528, filed on Jul. 23, 2019, and entitled “High Voltage Mn02|Zn and MnO2|Al Battery Using Permanganate and Gelled Alkaline Electrolyte,” and 3) U.S. Provisional Application No. 62/895,706, filed on Sep. 4, 2019, and entitled “Complete Solid State High Voltage Aqueous Battery with High Ionic Conductivity,” all three of which are incorporated herein by reference in their entirety for all purposes.

STATEMENT REGARDING GOVERNMENTALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

BACKGROUND

Aqueous batteries containing manganese dioxide as the cathode active material are ubiquitous in the modern world. It is widely marketed as a primary battery when paired with a zinc anode for use in household electronics, camera batteries, video game controller batteries, etc. The open circuit potential of these batteries are usually between 1.5-1.6V because of the use of alkaline electrolyte. Batteries containing acidic or neutral electrolyte are also marketed as Leclanche-type with the open circuit potential in a similar range as that of the alkaline battery.

Other batteries can compete with aqueous batteries. For example, lithium (Li)-ion batteries dominate the storage landscape for almost all types of applications. Lead acid batteries still compete in some niche markets and in developing countries because of its low cost, however, these are extremely toxic. Li-ion batteries greatest asset has been its high voltage, which has allowed it to be applied for mobile electronics to electric cars. However, it does contain elements like Li and cobalt (Co) which are known to be geopolitically very sensitive elements and have a very high cost. Cobalt also has ethical issues surrounding its toxic effect on miners and their families. Li-ion batteries also seem to have hit its practical intercalation limit, so there cannot be much gain in energy density from these batteries anymore.

SUMMARY

In some embodiments, a high voltage aqueous battery includes a cathode comprising a cathode electroactive material, an anode comprising an anode electroactive material, a catholyte solution in contact with the cathode, and a polymerized anolyte solution in contact with the anode. The catholyte solution can be polymerized, and an optional separator can be used between the anolyte and the catholyte.

In some embodiments, a high voltage aqueous battery comprises a cathode comprising a manganese dioxide, a spinel manganese oxide (Mn 3 O 4 ), or a manganese oxide (MnO), an anode comprising zinc, aluminum, magnesium, or iron, a polymerized catholyte solution in contact with the cathode, and a polymerized anolyte solution in contact with the anode.

In some embodiments, a high voltage aqueous battery comprises a cathode comprising lead oxide (PbO 2 ), an anode comprising zinc, aluminum, magnesium or iron, a polymerized catholyte solution in contact with the cathode, and a polymerized anolyte solution in contact with the anode.

These and other features will be more clearly understood from the following detailed description taken in conjunction with the accompanying claims.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the present disclosure and the advantages thereof, reference is now made to the following brief description, taken in connection with the accompanying drawings and detailed description, wherein like reference numerals represent like parts.

FIG. 1 is a schematic cross sectional view of a battery according to some embodiments.

FIG. 2 is a perspective view of the electrodes of a cylindrical or jelly roll battery according to some embodiments.

FIG. 3 is another schematic cross sectional view of a battery according to some embodiments.

FIG. 4 is still another schematic cross sectional view of a battery according to some embodiments.

FIG. 5 is yet another schematic cross sectional view of a battery according to some embodiments.

FIG. 6 illustrates a potential vs time plot for a test battery in which zinc is used as the anode as described in Example 1.

FIG. 7 illustrates a capacity vs cycle number plot for the test battery as described in Example 1.

FIG. 8 illustrates the Coulombic and energy efficiencies for the test battery as described in Example 1.

FIG. 9 illustrates a potential vs time curve for a test battery as described in Example 2.

FIG. 10 illustrates a primary discharge potential chart of a test battery as described in Example 3.

FIG. 11 illustrates a chart of the open circuit potential of three batteries with different electrolytes as described in Example 4.

FIG. 12 illustrates the first three discharge cycles for three batteries with different electrolytes as described in Example 4.

FIG. 13 illustrates the cycle life of a manganese dioxide battery using permanganate as described in Example 4.

FIG. 14 illustrates a potential vs discharge capacity chart for a test battery as described in Example 5.

FIG. 15 illustrates cycling curves for a manganese dioxide battery as described in Example 6.

FIG. 16 illustrates an SEM image of a charged electrode showing the manganese dioxide deposition as described in Example 6.

FIG. 17 illustrates an X-ray diffraction pattern of the cathode containing manganese dioxide at the end of the charge cycle as described in Example 6.

FIG. 18 schematically illustrates a voltage vs capacity chart showing various technologies.

FIG. 19 illustrates images of gelled manganese sulfate with sulfuric acid with various additives and pictures of gelled potassium hydroxide with a zinc mesh (lower left image) as described in Example 7.

FIG. 20 illustrates the open circuit potential of a test battery as described in Example 8.

FIG. 21 illustrates discharge curves for three test batteries as described in Example 8.

FIG. 22 illustrates the cycling performance of a test battery as described in Example 8.

FIG. 23 illustrates the open circuit potential of a test battery as described in Example 9.

FIG. 24 illustrates the discharge curve of a membrane-less test battery as described in Example 9.

FIG. 25 illustrates the cycling performance of a membrane-less test battery as described in Example 9.

DETAILED DESCRIPTION

In this disclosure, the terms “negative electrode” and “anode” are both used to mean “negative electrode.” Likewise, the terms “positive electrode” and “cathode” are both used to mean “positive electrode.” Reference to an “electrode” alone can refer to the anode, cathode, or both. Reference to the term “primary battery” (e.g., “primary battery,” “primary electrochemical cell,” or “primary cell”), refers to a cell or battery that after a single discharge is disposed of and replaced. Reference to the term “secondary battery” (e.g., “secondary battery,” “secondary electrochemical cell,” or “secondary cell”), refers to a cell or battery that can be recharged one or more times and reused. As used herein, a catholyte refers to an electrolyte solution in contact with the cathode without being in direct contact with the anode, and an “anolyte” refers to an electrolyte solution in contact with the anode without being in direct contact with the cathode.

The alkaline battery is widely used because of its superior storage properties and high ionic conductivity compared to acidic or neutral electrolyte. However, these batteries are used only once and then discarded because of the inactivity of its raw materials. Also, the energy extracted from these batteries can become low through use because the nominal voltage at which the capacity is extracted is around 1.1 to 1.2V. These characteristics curtail the use of this cheap, safe, and nonflammable and environmentally chemistry to small scale applications. If the voltage of the battery can be increased, a high fraction of the theoretical capacity of the raw materials can be accessed reversibly many times. If the cost of the battery can still be kept low, then this would represent a significant improvement in the field of energy storage systems as it would open the use of manganese dioxide-zinc batteries for use in applications that can have a larger impact on human life like grid storage applications, home power backup, use in mobile electronics, etc.

In some embodiments, a high voltage aqueous battery is disclosed, where manganese oxides (MnO 2 ), and in some embodiments lead oxide (PbO 2 ), is the primary cathode active material. The anode in this high voltage battery can be zinc (Zn), aluminum (Al), magnesium (Mg), and/or iron (Fe) active materials. The high voltage in the battery can be achieved by maintaining different pHs in the cathode and anode compartment of the battery, where the cathode is usually in acidic to neutral solutions and the anode can be in basic solution. In some embodiments, the high voltage aspect of the innovation can be achieved by polymerizing the alkaline electrolyte on the anode side and using an electrolyte comprising a permanganate on the cathode side. The resulting battery can be a stationary high voltage (2.8-4V) membrane-less aqueous battery containing manganese dioxide as the cathode. No flow or flow-assist condition is required for this battery as well. The manganese dioxide disclosed in this patent application can achieve 80-100% of its one electron (308 mAh/g) and two electron (617 mAh/g) capacity, respectively.

In some embodiments, the battery can be a complete solid state high voltage aqueous battery, which can deliver energy at a higher voltage than any battery that is currently available in the market. In this embodiment, the cathode can comprise manganese dioxide (MnO 2 ) or lead oxide (PbO 2 ) as the cathode active material, and the anode can comprise zinc (Zn), aluminum (Al), magnesium (Mg), and/or iron (Fe) as the anode active material. The high voltage in this battery can be achieved by maintaining different pHs in the cathode and anode compartment of the battery, where the cathode is usually in acidic to neutral solutions, while the anode is in basic/alkaline solution. The complete solid state aspect can be achieved by polymerizing both the cathode and anode electrolytes. The gelling of the electrolytes can result in a decrease in the ionic conductivity, which can be compensated for by increasing the ionic conductivity in the system by adding ammonium salts to the cathode electrolyte and potassium salts to the anode electrolyte. Better voltage characteristics can also be achieved by using additional dopants on the cathode electrode and/or electrolyte. This is the first disclosure of a fully solid state MnO 2 |Zn, MnO 2 |Al, MnO 2 |Mg and MnO 2 |Fe and PbO 2 |Zn, PbO 2 |Al, PbO 2 |Mg and PbO 2 |Fe high voltage aqueous battery (HiVAB), where potentials between 2.5 to 4V are seen for a MnO 2 |Zn system and potentials of ˜3V are seen for a PbO 2 |Zn system. The manganese dioxide disclosed in this patent application can achieve 80-100% of its one electron (308 mAh/g) and two electron (617 mAh/g) capacity, respectively. Other forms of manganese oxides can also be used as the cathode like spinel manganese oxide (Mn 3 O 4 , LiMn 2 O 4 , and/or ZnMn 2 O 4 ) and manganese oxide (MnO).

In some embodiments, a high voltage aqueous manganese dioxide battery with the ability to access its theoretical one electron (308 mAh/g) and two electron (617 mAh/g) capacity is provided. The high voltage can be achieved by creating a dual electrolyte battery, where the cathode is in acidic or near neutral electrolyte, while the anode is in basic electrolyte. The batteries can be constructed in several different manners. In some embodiments, the cathode can have a liquid catholyte comprising of acidic or neutral solution, and the anode can be in contact with an anolyte that is a polymerized or gelled electrolyte. The use of a separator with this type of battery is optional, and in some embodiments, the separator is not present between the catholyte and the anolyte. In some embodiments, the battery can comprise a liquid catholyte and a polymerized or gelled anolyte with a separator disposed between the catholyte and anolyte. In some embodiments, both the catholyte and the anolyte can be polymerized or gelled, and a separator may not be placed between the catholyte and the anolyte. In still other embodiments, both the catholyte and the anolyte can be polymerized or gelled and a separator can be disposed between the catholyte and the anolyte. Each of these embodiments is described in more detail herein.

Referring to FIG. 1 , a battery 10 can have a housing 7 , a cathode 12 , which can include a cathode current collector 1 and a cathode material 2 , and an anode 13 . In some embodiments, the anode 13 can comprise an anode current collector 4 , and an anode material 5 . It is noted that the scale of the components in FIG. <

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a filing under 35 U.S.C. 371 as the National Stage of International Application No. PCT/US2020/039927, filed on Jun. 26, 2020 and entitled, “HIGH VOLTAGE BATTERIES USING GELLED ELECTROLYTE,” which claims priority to and claims the benefit of: 1) U.S. Provisional Application No. 62/867,959, filed on Jun. 28, 2019, and entitled “Membrane-Less High Voltage Aqueous Manganese Dioxide Battery,” 2) U.S. Provisional Application No. 62/877,528, filed on Jul. 23, 2019, and entitled “High Voltage Mn02|Zn and MnO2|Al Battery Using Permanganate and Gelled Alkaline Electrolyte,” and 3) U.S. Provisional Application No. 62/895,706, filed on Sep. 4, 2019, and entitled “Complete Solid State High Voltage Aqueous Battery with High Ionic Conductivity,” all three of which are incorporated herein by reference in their entirety for all purposes.

STATEMENT REGARDING GOVERNMENTALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

BACKGROUND

Aqueous batteries containing manganese dioxide as the cathode active material are ubiquitous in the modern world. It is widely marketed as a primary battery when paired with a zinc anode for use in household electronics, camera batteries, video game controller batteries, etc. The open circuit potential of these batteries are usually between 1.5-1.6V because of the use of alkaline electrolyte. Batteries containing acidic or neutral electrolyte are also marketed as Leclanche-type with the open circuit potential in a similar range as that of the alkaline battery.

Other batteries can compete with aqueous batteries. For example, lithium (Li)-ion batteries dominate the storage landscape for almost all types of applications. Lead acid batteries still compete in some niche markets and in developing countries because of its low cost, however, these are extremely toxic. Li-ion batteries greatest asset has been its high voltage, which has allowed it to be applied for mobile electronics to electric cars. However, it does contain elements like Li and cobalt (Co) which are known to be geopolitically very sensitive elements and have a very high cost. Cobalt also has ethical issues surrounding its toxic effect on miners and their families. Li-ion batteries also seem to have hit its practical intercalation limit, so there cannot be much gain in energy density from these batteries anymore.

SUMMARY

In some embodiments, a high voltage aqueous battery includes a cathode comprising a cathode electroactive material, an anode comprising an anode electroactive material, a catholyte solution in contact with the cathode, and a polymerized anolyte solution in contact with the anode. The catholyte solution can be polymerized, and an optional separator can be used between the anolyte and the catholyte.

In some embodiments, a high voltage aqueous battery comprises a cathode comprising a manganese dioxide, a spinel manganese oxide (Mn 3 O 4 ), or a manganese oxide (MnO), an anode comprising zinc, aluminum, magnesium, or iron, a polymerized catholyte solution in contact with the cathode, and a polymerized anolyte solution in contact with the anode.

In some embodiments, a high voltage aqueous battery comprises a cathode comprising lead oxide (PbO 2 ), an anode comprising zinc, aluminum, magnesium or iron, a polymerized catholyte solution in contact with the cathode, and a polymerized anolyte solution in contact with the anode.

These and other features will be more clearly understood from the following detailed description taken in conjunction with the accompanying claims.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the present disclosure and the advantages thereof, reference is now made to the following brief description, taken in connection with the accompanying drawings and detailed description, wherein like reference numerals represent like parts.

FIG. 1 is a schematic cross sectional view of a battery according to some embodiments.

FIG. 2 is a perspective view of the electrodes of a cylindrical or jelly roll battery according to some embodiments.

FIG. 3 is another schematic cross sectional view of a battery according to some embodiments.

FIG. 4 is still another schematic cross sectional view of a battery according to some embodiments.

FIG. 5 is yet another schematic cross sectional view of a battery according to some embodiments.

FIG. 6 illustrates a potential vs time plot for a test battery in which zinc is used as the anode as described in Example 1.

FIG. 7 illustrates a capacity vs cycle number plot for the test battery as described in Example 1.

FIG. 8 illustrates the Coulombic and energy efficiencies for the test battery as described in Example 1.

FIG. 9 illustrates a potential vs time curve for a test battery as described in Example 2.

FIG. 10 illustrates a primary discharge potential chart of a test battery as described in Example 3.

FIG. 11 illustrates a chart of the open circuit potential of three batteries with different electrolytes as described in Example 4.

FIG. 12 illustrates the first three discharge cycles for three batteries with different electrolytes as described in Example 4.

FIG. 13 illustrates the cycle life of a manganese dioxide battery using permanganate as described in Example 4.

FIG. 14 illustrates a potential vs discharge capacity chart for a test battery as described in Example 5.

FIG. 15 illustrates cycling curves for a manganese dioxide battery as described in Example 6.

FIG. 16 illustrates an SEM image of a charged electrode showing the manganese dioxide deposition as described in Example 6.

FIG. 17 illustrates an X-ray diffraction pattern of the cathode containing manganese dioxide at the end of the charge cycle as described in Example 6.

FIG. 18 schematically illustrates a voltage vs capacity chart showing various technologies.

FIG. 19 illustrates images of gelled manganese sulfate with sulfuric acid with various additives and pictures of gelled potassium hydroxide with a zinc mesh (lower left image) as described in Example 7.

FIG. 20 illustrates the open circuit potential of a test battery as described in Example 8.

FIG. 21 illustrates discharge curves for three test batteries as described in Example 8.

FIG. 22 illustrates the cycling performance of a test battery as described in Example 8.

FIG. 23 illustrates the open circuit potential of a test battery as described in Example 9.

FIG. 24 illustrates the discharge curve of a membrane-less test battery as described in Example 9.

FIG. 25 illustrates the cycling performance of a membrane-less test battery as described in Example 9.

DETAILED DESCRIPTION

In this disclosure, the terms “negative electrode” and “anode” are both used to mean “negative electrode.” Likewise, the terms “positive electrode” and “cathode” are both used to mean “positive electrode.” Reference to an “electrode” alone can refer to the anode, cathode, or both. Reference to the term “primary battery” (e.g., “primary battery,” “primary electrochemical cell,” or “primary cell”), refers to a cell or battery that after a single discharge is disposed of and replaced. Reference to the term “secondary battery” (e.g., “secondary battery,” “secondary electrochemical cell,” or “secondary cell”), refers to a cell or battery that can be recharged one or more times and reused. As used herein, a catholyte refers to an electrolyte solution in contact with the cathode without being in direct contact with the anode, and an “anolyte” refers to an electrolyte solution in contact with the anode without being in direct contact with the cathode.

The alkaline battery is widely used because of its superior storage properties and high ionic conductivity compared to acidic or neutral electrolyte. However, these batteries are used only once and then discarded because of the inactivity of its raw materials. Also, the energy extracted from these batteries can become low through use because the nominal voltage at which the capacity is extracted is around 1.1 to 1.2V. These characteristics curtail the use of this cheap, safe, and nonflammable and environmentally chemistry to small scale applications. If the voltage of the battery can be increased, a high fraction of the theoretical capacity of the raw materials can be accessed reversibly many times. If the cost of the battery can still be kept low, then this would represent a significant improvement in the field of energy storage systems as it would open the use of manganese dioxide-zinc batteries for use in applications that can have a larger impact on human life like grid storage applications, home power backup, use in mobile electronics, etc.

In some embodiments, a high voltage aqueous battery is disclosed, where manganese oxides (MnO 2 ), and in some embodiments lead oxide (PbO 2 ), is the primary cathode active material. The anode in this high voltage battery can be zinc (Zn), aluminum (Al), magnesium (Mg), and/or iron (Fe) active materials. The high voltage in the battery can be achieved by maintaining different pHs in the cathode and anode compartment of the battery, where the cathode is usually in acidic to neutral solutions and the anode can be in basic solution. In some embodiments, the high voltage aspect of the innovation can be achieved by polymerizing the alkaline electrolyte on the anode side and using an electrolyte comprising a permanganate on the cathode side. The resulting battery can be a stationary high voltage (2.8-4V) membrane-less aqueous battery containing manganese dioxide as the cathode. No flow or flow-assist condition is required for this battery as well. The manganese dioxide disclosed in this patent application can achieve 80-100% of its one electron (308 mAh/g) and two electron (617 mAh/g) capacity, respectively.

In some embodiments, the battery can be a complete solid state high voltage aqueous battery, which can deliver energy at a higher voltage than any battery that is currently available in the market. In this embodiment, the cathode can comprise manganese dioxide (MnO 2 ) or lead oxide (PbO 2 ) as the cathode active material, and the anode can comprise zinc (Zn), aluminum (Al), magnesium (Mg), and/or iron (Fe) as the anode active material. The high voltage in this battery can be achieved by maintaining different pHs in the cathode and anode compartment of the battery, where the cathode is usually in acidic to neutral solutions, while the anode is in basic/alkaline solution. The complete solid state aspect can be achieved by polymerizing both the cathode and anode electrolytes. The gelling of the electrolytes can result in a decrease in the ionic conductivity, which can be compensated for by increasing the ionic conductivity in the system by adding ammonium salts to the cathode electrolyte and potassium salts to the anode electrolyte. Better voltage characteristics can also be achieved by using additional dopants on the cathode electrode and/or electrolyte. This is the first disclosure of a fully solid state MnO 2 |Zn, MnO 2 |Al, MnO 2 |Mg and MnO 2 |Fe and PbO 2 |Zn, PbO 2 |Al, PbO 2 |Mg and PbO 2 |Fe high voltage aqueous battery (HiVAB), where potentials between 2.5 to 4V are seen for a MnO 2 |Zn system and potentials of ˜3V are seen for a PbO 2 |Zn system. The manganese dioxide disclosed in this patent application can achieve 80-100% of its one electron (308 mAh/g) and two electron (617 mAh/g) capacity, respectively. Other forms of manganese oxides can also be used as the cathode like spinel manganese oxide (Mn 3 O 4 , LiMn 2 O 4 , and/or ZnMn 2 O 4 ) and manganese oxide (MnO).

In some embodiments, a high voltage aqueous manganese dioxide battery with the ability to access its theoretical one electron (308 mAh/g) and two electron (617 mAh/g) capacity is provided. The high voltage can be achieved by creating a dual electrolyte battery, where the cathode is in acidic or near neutral electrolyte, while the anode is in basic electrolyte. The batteries can be constructed in several different manners. In some embodiments, the cathode can have a liquid catholyte comprising of acidic or neutral solution, and the anode can be in contact with an anolyte that is a polymerized or gelled electrolyte. The use of a separator with this type of battery is optional, and in some embodiments, the separator is not present between the catholyte and the anolyte. In some embodiments, the battery can comprise a liquid catholyte and a polymerized or gelled anolyte with a separator disposed between the catholyte and anolyte. In some embodiments, both the catholyte and the anolyte can be polymerized or gelled, and a separator may not be placed between the catholyte and the anolyte. In still other embodiments, both the catholyte and the anolyte can be polymerized or gelled and a separator can be disposed between the catholyte and the anolyte. Each of these embodiments is described in more detail herein.

Referring to FIG. 1 , a battery 10 can have a housing 7 , a cathode 12 , which can include a cathode current collector 1 and a cathode material 2 , and an anode 13 . In some embodiments, the anode 13 can comprise an anode current collector 4 , and an anode material 5 . It is noted that the scale of the components in FIG. 1 may not be exact as the features are illustrates to clearly show the electrolyte around the anode 13 and the cathode 12 . FIG. 1 shows a prismatic battery arrangement having a single anode 13 and cathode 12 . In another embodiment, the battery can be a cylindrical battery (e.g., as shown in FIG. 2 ) having the electrodes arranged concentrically or in a rolled configuration in which the anode and cathode are layered and then rolled to form a jelly roll configuration. The cathode current collector 1 and cathode material 2 are collectively called either the cathode 12 or the positive electrode 12 , as shown in FIG. 2 . Similarly, the anode material 5 with the optional anode current collector 4 can be collectively called either the anode 13 or the negative electrode 13 . A catholyte 3 can be in contact with the cathode 12 , and an anolyte 6 can be in contact with the anode 13 . As described in more detail herein, the catholyte 3 and/or the anolyte 6 can be polymerized or gelled to prevent mixing between the two electrolyte solutions.

In some embodiments, the battery 10 can comprise one or more cathodes 12 and one or more anodes 13 . When a plurality of anodes 13 and/or a plurality of cathodes 12 are present, the electrodes can be configured in a layered configuration such that the electrodes alternate (e.g., anode, cathode, anode, etc.). Any number of anodes 13 and/or cathodes 12 can be present to provide a desired capacity and/or output voltage. In the jellyroll configuration, the battery 10 may only have one cathode 12 and one anode 13 in a rolled configuration such that a cross section of the battery 10 includes a layered configuration of alternating electrodes.

In an embodiment, housing 7 comprises a molded box or container that is generally non-reactive with respect to the electrolyte solutions in the battery 10 , including the catholyte 3 and the anolyte 6 . In an embodiment, the housing 7 comprises a polypropylene molded box, an acrylic polymer molded box, or the like.

The cathode 12 can comprise a mixture of components including an electrochemically active material, a binder, a conductive material, and/or one or more additional components that can serve to improve the lifespan, rechargeability, and electrochemical properties of the cathode 12 . The cathode can comprise an active cathode material 2 (e.g., an electroactive material). Suitable cathode materials 2 can include, but are not limited to, manganese dioxide, copper manganese oxide, hausmannite, manganese oxide, copper intercalated bismuth birnessite, birnessite, todokorite, ramsdellite, pyrolusite, pyrochroite, lead, lead hydroxide, lead oxide, or any combination thereof. The electroactive component in the cathode material 2 can be between 1 and 99 wt. % of the weight of the cathode material 2 , and the conductive additive can be between 1 and 99 wt. %.

In some embodiments, the active cathode material can based on one or many polymorphs of MnO 2 , including electrolytic (EMD), α-MnO 2 , β-MnO 2 , γ-MnO 2 , δ-MnO 2 , ε-MnO 2 , or λ-MnO 2 . Other forms of MnO 2 can also be present such as pyrolusite, birnessite, ramsdellite, hollandite, romanechite, todorkite, lithiophorite, chalcophanite, sodium or potassium rich birnessite, cryptomelane, buserite, manganese oxyhydroxide (MnOOH), α-MnOOH, γ-MnOOH, β-MnOOH, manganese hydroxide [Mn(OH) 2 ], partially or fully protonated manganese dioxide, Mn 3 O 4 , Mn 2 O 3 , bixbyite, MnO, lithiated manganese dioxide (LiMn 2 O 4 ), CuMn 2 O 4 , zinc manganese dioxide, or any combination therof. In general the cycled form of manganese dioxide in the cathode can have a layered configuration, which in some embodiment can comprise δ-MnO 2 that is interchangeably referred to as birnessite. If non-birnessite polymorphic forms of manganese dioxide are used, these can be converted to birnessite in-situ by one or more conditioning cycles as described in more details below. For example, a full or partial discharge to the end of the MnO 2 second electron stage (e.g., between about 20% to about 100% of the 2 nd electron capacity of the cathode) may be performed and subsequently recharging back to its Mn 4+ state, resulting in birnessite-phase manganese dioxide.

The addition of a conductive additive such as conductive carbon enables high loadings of an electroactive material in the cathode material, resulting in high volumetric and gravimetric energy density. The conductive additive can be present in a concentration between about 1-30 wt. %. In some embodiments, the conductive additive can comprise 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, or a combination thereof. Higher loadings of the electroactive material in the cathode are, in some embodiments, desirable to increase the energy density. Other examples of conductive carbon include TIMREX Primary Synthetic Graphite (all types), TIMREX Natural Flake Graphite (all types), TIMREX MB, MK, MX, KC, B, LB Grades(examples, KS15, KS44, KC44, MB15, MB25, MK15, MK25, MK44, MX15, MX25, BNB90, LB family) TIMREX Dispersions; ENASCO 150G, 210G, 250G, 260G, 350G, 150P, 250P; SUPER P , SUPER P Li, carbon black (examples include Ketjenblack EC-300J, Ketjenblack EC-600JD, Ketjenblack EC-600JD powder), acetylene black, carbon nanotubes (single or multi-walled), Zenyatta graphite, and combinations thereof. When the electroactive material comprises manganese, the birnessite discharge reaction comprises a dissolution-precipitation reaction where Mn 3+ ions become soluble and precipitate out on the conductive carbon as Mn 2+ . This second electron process can involve the formation of a non-conductive manganese hydroxide [Mn(OH) 2 ] layer on the conductive graphite.

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

The cathode material 2 can also comprise a conductive component. The addition of a conductive component such as metal additives to the cathode material may be accomplished by addition of one or more metal powders such as nickel powder to the cathode mixture. The conductive metal component can be present in a concentration of between about 0-30 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 can be added as an oxide and/or salt. For example, the conductive component can be cobalt oxide, cobalt hydroxide, lead oxide, lead hydroxide, or a combination thereof. In some embodiments, a second conductive metal component is added to act as a supportive conductive backbone for the first and second electron reactions to take place. The second electron reaction has a dissolution-precipitation reaction where Mn 3+ ions become soluble in the electrolyte and precipitate out on the graphite resulting in an electrochemical reaction and the formation of manganese hydroxide [Mn(OH) 2 ] which is non-conductive. This ultimately results in a capacity fade in subsequent cycles. Suitable second component include transition metals like Ni, Co, Fe, Ti and metals like Ag, Au, Al, Ca. Oxides and salts of such metals are also suitable. Transition metals like Co can also help in reducing the solubility of Mn 3+ ions. Such conductive metal components may be incorporated into the electrode by chemical means or by physical means (e.g. ball milling, mortar/pestle, spex mixture). An example of such an electrode comprises 5-95% birnessite, 5-95% conductive carbon, 0-50% second conductive metal component, and 1-10% binder.

In some embodiments, a binder can be used with the cathode material 2 . The binder can be present in a concentration of between about 0-10 wt. %. In some embodiments, the binder comprises water-soluble cellulose-based hydrogels, which can be used as thickeners and strong binders, and have been cross-linked with good mechanical strength and with conductive polymers. The binder may also be a cellulose film sold as cellophane. The binders can be made by physically cross-linking the water-soluble cellulose-based hydrogels with a polymer through repeated cooling and thawing cycles. In some embodiments, the binder can comprise a 0-10 wt. % carboxymethyl cellulose (CMC) solution cross-linked with 0-10 wt. % polyvinyl alcohol (PVA) on an equal volume basis. The binder, compared to the traditionally-used TEFLON®, shows superior performance. TEFLON® is a very resistive material, but its use in the industry has been widespread due to its good rollable properties. This, however, does not rule out using TEFLON® as a binder. Mixtures of TEFLON® with the aqueous binder and some conductive carbon were used to create rollable binders. Using the aqueous-based binder helps in achieving a significant fraction of the two electron capacity with minimal capacity loss over many cycles. In some embodiments, the binder can be water-based, have superior water retention capabilities, adhesion properties, and help to maintain the conductivity relative to an identical cathode using a TEFLON® binder instead. Examples of hydrogels can include, but are not limited to, methyl cellulose (MC), carboxymethyl cellulose (CMC), hydroypropyl cellulose (HPH), hydroypropylmethyl cellulose (HPMC), hydroxethylmethyl cellulose (HEMC), carboxymethylhydroxyethyl cellulose and hydroxyethyl cellulose (HEC). Examples of crosslinking polymers include polyvinyl alcohol, polyvinylacetate, polyaniline, polyvinylpyrrolidone, polyvinylidene fluoride and polypyrrole. In some embodiments, a 0-10 wt. % solution of water-cased cellulose hydrogen can be cross linked with a 0-10% wt solution of crosslinking polymers by, for example, repeated freeze/thaw cycles, radiation treatment or chemical agents (e.g. epichlorohydrin). The aqueous binder may be mixed with 0-5% TEFLON® to improve manufacturability.

The cathode material 2 can also comprise additional elements. The additional elements can be included in the cathode material including a bismuth compound and/or copper/copper compounds, which together allow improved galvanostatic battery cycling of the cathode. When present as birnessite, the copper and/or bismuth can be incorporated into the layered nanostructure of the birnessite. The resulting birnessite cathode material can exhibit improved cycling and long term performance with the copper and bismuth incorporated into the crystal and nanostructure of the birnessite.

The bismuth compound can be incorporated into the cathode 12 as an inorganic or organic salt of bismuth (

oxidation states

5, 4, 3, 2, or 1), as a bismuth oxide, or as bismuth metal (i.e. elemental bismuth). The bismuth compound can be present in the cathode material at a concentration between about 1-20 wt. % of the weight of the cathode material 2 . Examples of inorganic bismuth compounds include bismuth chloride, bismuth bromide, bismuth fluoride, bismuth iodide, bismuth sulfate, bismuth nitrate, bismuth trichloride, bismuth citrate, bismuth telluride, bismuth selenide, bismuth subsalicylate, bismuth neodecanoate, bismuth carbonate, bismuth subgallate, bismuth strontium calcium copper oxide, bismuth acetate, bismuth trifluoromethanesulfonate, bismuth nitrate oxide, bismuth gallate hydrate, bismuth phosphate, bismuth cobalt zinc oxide, bismuth sulphite agar, bismuth oxychloride, bismuth aluminate hydrate, bismuth tungsten oxide, bismuth lead strontium calcium copper oxide, bismuth antimonide, bismuth antimony telluride, bismuth oxide yittia stabilized, bismuth-lead alloy, ammonium bismuth citrate, 2-napthol bismuth salt, duchloritri(o-tolyl)bismuth, dichlordiphenyl(p-tolyl)bismuth, triphenylbismuth, or any combination thereof.

The copper compound can be incorporated into the cathode 12 as an organic or inorganic salt of copper (

oxidation states

1,2,3 or 4), as a copper oxide, or as copper metal (i.e., elemental copper). The copper compound can be present in a concentration between about 1-70 wt. % of the weight of the cathode material 2 . In some embodiments, the copper compound is present in a concentration between about 5-50 wt. % of the weight of the cathode material 2 . In other embodiments, the copper compound is present in a concentration between about 10-50 wt. % of the weight of the cathode material 2 . In yet other embodiments, the copper compound is present in a concentration between about 5-20 wt. % of the weight of the cathode material 2 . Examples of copper compounds include copper and copper salts such as copper aluminum oxide, copper (I) oxide, copper (II) oxide and/or copper salts in a +1, +2, +3, or +4 oxidation state including, but not limited to, copper nitrate, copper sulfate, copper chloride, etc. The effect of copper is to alter the oxidation and reduction voltages of bismuth. This results in a cathode with full reversibility during galvanostatic cycling, as compared to a bismuth-modified MnO 2 which cannot withstand galvanostatic cycling as well.

The cathodes 12 can be produced using methods implementable in large-scale manufacturing. For a MnO 2 cathode, the cathode 12 can be capable of delivering the full second electron capacity of the MnO 2 . Excellent rechargeable performance can be achieved for both low and high loadings of MnO 2 in the mixed material, allowing the cell/battery to achieve very high practical energy densities. In some embodiments, the cathode material can comprises 2-30% wt conductive carbon, 0-30% conductive metal additive, 1-70% wt. copper compound, 1-20% wt bismuth compound, 0-10 wt. % binder and birnessite or EMD. In another embodiment the cathode material comprises 2-30 wt. % conductive carbon, 0-30% conductive metal additive, 1-20% wt bismuth compound, 0-10 wt. % binder and birnessite or EMD. In one embodiment, the cathode material consists essentially of 2-30 wt. % conductive carbon, 0-30% conductive metal additive, 1-70% wt. copper compound, 1-20 wt. % bismuth compound, 0-10% wt binder and the balance birnessite or EMD. In another embodiment the cathode material consists essentially of 2-30 wt. % conductive carbon, 0-30% conductive metal additive, 1-20% wt bismuth compound, 0-10 wt. % binder and the balance birnessite or EMD.

The resulting cathode may have a porosity in the range of 20%-85% as determined by mercury infiltration porosimetry. The porosity can be measured according to ASTM D4284-12 “Standard Test Method for Determining Pore Volume Distribution of Catalysts and Catalyst Carriers by Mercury Intrusion Porosimetry.”

The cathode material 2 can be formed on a cathode current collector 1 formed from a conductive material that serves as an electrical connection between the cathode material and an external electrical connection or connections. In some embodiments, the cathode current collector 1 can be, for example, carbon, lead, nickel, steel (e.g., stainless steel, etc.), nickel-coated steel, nickel plated copper, tin-coated steel, copper plated nickel, silver coated 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 can comprise a carbon felt or conductive polymer mesh. The cathode current collector may be formed into a mesh (e.g., an expanded mesh, woven mesh, etc.), perforated metal, foam, foil, felt, fibrous, porous block architecture, perforated foil, wire screen, a wrapped assembly, or any combination thereof. In some embodiments, the current collector can be formed into or form a part of a pocket assembly, where the pocket can hold the cathode material 2 within the current collector 1 . A tab (e.g., a portion of the cathode current collector 1 extending outside of the cathode material 2 as shown at the top of the cathode 12 in FIG. 1 ) can be coupled to the current collector to provide an electrical connection between an external source and the current collector.

The cathode material 2 can be pressed onto the cathode current collector 1 to form the cathode 12 . For example, the cathode material 2 can be adhered to the cathode current collector 1 by pressing at, for example, a pressure between 1,000 psi and 20,000 psi (between 6.9×10 6 and 1.4×10 8 Pascals). The cathode material 2 may be adhered to the cathode current collector 1 as a paste. A tab of the cathode current collector 1 , when present, can extend outside of the housing 7 to form the current collector tab.

The catholyte 3 can be disposed in the housing 10 in contact with the cathode material 2 and the anolyte 6 . In the embodiment shown in FIG. 1 , the anolyte 6 can be polymerized or gelled, and the catholyte 3 can be a liquid. The polymerization of the anolyte 6 can prevent mixing between the catholyte 3 and the anolyte 6 even when the catholyte 3 is a liquid.

In some embodiments, the catholyte can comprise an acid such as a mineral acid (e.g., hydrochloric acid, nitric acid, sulfuric acid, etc.). For acid catholyte compositions, the acid concentration can be between about 0 M and about 16 M. In some embodiments, the catholyte solution can comprise a solution comprising potassium permanganate, sodium permanganate, lithium permanganate, calcium permanganate, manganese sulfate, manganese chloride, manganese nitrate, manganese perchlorate, manganese acetate, manganese triflate, manganese carbonate, manganese oxalate, manganese fluorosilicate, manganese ferrocyanide, manganese bromide, magnesium sulfate, zinc sulfate, zinc triflate, zinc acetate, zinc nitrate, bismuth chloride, bismuth nitrate, nitric acid, sulfuric acid, hydrochloric acid, sodium sulfate, potassium sulfate, sodium hydroxide, potassium hydroxide, titanium sulfate, titanium chloride, lithium nitrate, lithium chloride, lithium bromide, lithium bicarbonate, lithium acetate, lithium sulfate, lithium nitrite, lithium hydroxide, lithium perchlorate, lithium oxalate, lithium fluoride, lithium carbonate, lithium sulfate, lithium bromate, or any combination thereof. For example, the cathode solution can comprise manganese sulfate mixed with sulfuric acid or potassium permanganate mixed with sulfuric acid. Other dopants to this solution can be zinc sulfate, lead sulfate, titanium disulfide, titanium sulfate hydrate, silver sulfate, cobalt sulfate, and nickel sulfate. The catholyte can be an acidic or neutral solution, and the pH of the catholyte can be between −1.2 and 7. The catholyte can be used in conditions having temperatures ranging between 0 and 200° C.

In some embodiments, the catholyte can comprise a permanganate. Permanganates have a high positive potential. This can allow the overall cell potential to be increased within the battery 10 . When present, the permanganate can be present in a molar ratio of an acid (e.g., a mineral acid such a hydrochloric acid, sulfuric acid, etc.) to permanganate of between about 1:1 to about 1:6, or between about 1:2 to about 1:4, or about 1:3, though the exact amount can vary based on the expected operation conditions of the battery 10 . The concentration of the permanganate (e.g., potassium permanganate or a salt of permanganate, etc.) can be greater than 0 and less than or equal to 5 M. In some embodiments, the catholyte solution comprises sulfuric acid, hydrochloric acid or nitric acid at a concentration greater than 0 and less than or equal to 16M. The use of a permanganate can be advantageous for creating a high voltage battery such that when the use of a catholyte with permanganates is combined with a very negative anode potential, the resulting batter can have an voltage of approximately 2.8V when the cathode and anode are Mno 2 |Zn and a voltage of approximately 4V when the cathode and anode are Mno 2 |Al.

In some embodiments, the electroactive component of the anode material 5 can comprise zinc, aluminum, magnesium, iron, or any combination thereof. In some embodiments, the anode material 5 can comprise iron oxide, iron hydroxide, bismuth oxide, bismuth, indium oxide, indium hydroxide, indium, copper, copper oxide, copper hydroxide, a manganese oxide (e.g., Mn 3 O 4 , Mn 2 O 3 , MnO 2 , combinations thereof, etc.), or combinations thereof. In alkaline electrolytes, the anode material 5 can have relatively negative reduction potential that allow the voltage in the battery to be relatively high. When the manganese dioxide is in acidic solution and the anode material 5 comprises zinc or aluminum in contact with a basic solution, a battery voltage of &gt;2.4-4V can be achieved, which makes the battery equivalent or better to variations of lithium-ion, lithium metal, sodium-ion, sodium metal, potassium-ion, potassium metal, calcium-ion, calcium metal, magnesium metal and metal-sulfur chemistry, which are usually flammable, toxic, and very expensive.

In some embodiments, the anode material 5 can comprise zinc, which can be present as elemental zinc and/or zine oxide. In some embodiments, the Zn anode mixture comprises Zn, zinc oxide (ZnO), an electronically conductive material, and a binder. The Zn may be present in the anode material 5 in an amount of from about 50 wt. % to about 90 wt. %, alternatively from about 60 wt. % to about 80 wt. %, or alternatively from about 65 wt. % to about 75 wt. %, based on the total weight of the anode material. Additional elements that can be in the anode in addition to the zinc or in place of the zinc include, but are not limited to, lithium, aluminum, magnesium, iron, cadmium, or any combination thereof, where each element can be present in amounts that are the same or similar to that of the zinc described herein.

In some embodiments, the anode material 5 can comprise zinc oxide (ZnO), which may be present in an amount of from about 5 wt. % to about 20 wt. %, alternatively from about 5 wt. % to about 15 wt. %, or alternatively from about 5 wt. % to about 10 wt. %, based on the total weight of anode material. As will be appreciated by one of skill in the art, and with the help of this disclosure, the purpose of the ZnO in the anode mixture is to provide a source of Zn during the recharging steps, and the zinc present can be converted between zinc and zinc oxide during charging and discharging phases.

<div id="p-0063" num="0062" class=

CLAIMS

Claims ( 35 )

What is claimed is:

1. A battery, wherein the battery is a high voltage aqueous battery, comprising:

a cathode comprising a cathode electroactive material;

an anode comprising an anode electroactive material;

a catholyte solution in contact with the cathode, wherein the catholyte solution is not in contact with the anode; and

a polymerized anolyte solution in contact with the anode,

wherein the cathode comprises lead oxide (PbO 2 );

wherein the anode comprises zinc, aluminum, magnesium, or iron; and

wherein the catholyte solution is a polymerized catholyte solution.

2. The battery of claim 1 , wherein the cathode electroactive material further comprises manganese dioxide.

3. The battery of claim 1 , wherein the anode further comprises iron oxide, iron hydroxide, bismuth oxide, bismuth, indium oxide, indium hydroxide, indium, copper, copper oxide, copper hydroxide, a manganese oxide, or any combination thereof.

4. The battery as recited in claim 1 , wherein the cathode and the anode each contain a current collector made of carbon, lead, copper, nickel, silver, bismuth, titanium, magnesium, aluminum, gold, or a combination thereof.

5. The battery of claim 4 , wherein the current collector is a mesh, foil, foam, felt, fibrous, a porous block architecture, or a combination thereof.

6. The battery of claim 1 , wherein the polymerized catholyte solution comprises potassium permanganate, sodium permanganate, lithium permanganate, manganese sulfate, manganese chloride, manganese nitrate, manganese perchlorate, manganese acetate, manganese triflate, manganese carbonate, manganese oxalate, manganese fluorosilicate, manganese ferrocyanide, manganese bromide, magnesium sulfate, zinc sulfate, zinc triflate, zinc acetate, zinc nitrate, bismuth chloride, bismuth nitrate, nitric acid, sulfuric acid, hydrochloric acid, sodium sulfate, potassium sulfate, sodium hydroxide, potassium hydroxide, titanium sulfate, titanium chloride, lithium nitrate, lithium chloride, lithium bromide, lithium bicarbonate, lithium acetate, lithium sulfate, lithium nitrate, lithium nitrite, lithium hydroxide, lithium perchlorate, lithium oxalate, lithium fluoride, lithium carbonate, lithium sulfate, lithium bromate, or a combination thereof.

7. The battery of claim 1 , wherein the polymerized catholyte solution has a pH between −1.2 and 7.

8. The battery of claim 1 , wherein the polymerized catholyte solution comprises a salt of permanganate at a concentration greater than 0 and less than or equal to 5M.

9. The battery of claim 1 , wherein the polymerized catholyte solution comprises sulfuric acid, hydrochloric acid, or nitric acid at a concentration greater than 0 and less than or equal to 16M.

10. The battery of claim 1 , wherein the polymerized catholyte solution comprises a salt of permanganate and an acid, wherein a molar ratio of the salt of permanganate to the acid is 1:3.

11. The battery of claim 1 , wherein the cathode electroactive material further comprises carbon.

12. The battery of claim 11 , wherein the carbon is graphite, carbon fiber, carbon black, acetylene black, single walled carbon nanotubes, multi-walled carbon nanotubes, nickel or copper coated carbon nanotubes, dispersions of single walled carbon nanotubes, dispersions of multi-walled carbon nanotubes, graphene, graphyne, graphene oxide, or a combination thereof.

13. The battery of claim 1 , wherein the polymerized anolyte solution comprises zinc sulfate, zinc chloride, zinc acetate, zinc carbonate, zinc chlorate, zinc fluoride, zinc formate, zinc nitrate, zinc oxalate, zinc sulfite, zinc tartrate, zinc cyanide, zinc oxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium chloride, sodium chloride, potassium fluoride, lithium nitrate, lithium chloride, lithium bromide, lithium bicarbonate, lithium acetate, lithium sulfate, lithium permanganate, lithium nitrite, lithium perchlorate, lithium oxalate, lithium fluoride, lithium carbonate, lithium bromate, acrylic acid, N,N′-Methylenebisacrylamide, potassium persulfate, ammonium persulfate, sodium persulfate, or a combination thereof.

14. The battery of claim 1 , wherein the polymerized anolyte solution has a pH between 10 and 15.13.

15. The battery of claim 1 , wherein the anode is a foil architecture, a mesh architecture, a perforated architecture, a foam architecture, a felt architecture, or a powder architecture.

16. The battery of claim 1 , further comprising:

a separator disposed between the polymerized catholyte solution and the polymerized anolyte solution.

17. The battery of claim 16 , wherein the separator is polyvinyl alcohol, a composite of polyvinyl alcohol and graphene oxide, a microporous separator, or a combination thereof.

18. The battery of claim 1 , wherein the battery has an open circuit potential between 2V and 4V.

19. A high voltage aqueous battery comprising:

a cathode comprising a manganese dioxide, a spinel manganese oxide (Mn 3 O 4 ), or a manganese oxide (MnO);

an anode comprising zinc, aluminum, magnesium, or iron;

a polymerized catholyte solution in contact with the cathode; and

a polymerized anolyte solution in contact with the anode,

wherein the polymerized catholyte solution comprises manganese sulfate, ammonium chloride, ammonium sulfate, manganese acetate, or a salt of permanganate at a concentration between 0 and 10M.

20. The battery of claim 19 , wherein the polymerized catholyte solution further comprises sulfuric acid, hydrochloric acid, or nitric acid at a concentration between 0 and 16M.

21. The battery of claim 19 , wherein the polymerized catholyte solution comprises the salt of permanganate and an acid, wherein the volumetric ratio of the salt of permanganate to the acid is 5:1 to 1:5.

22. The battery of claim 19 , wherein the polymerized catholyte solution comprises manganese sulfate, ammonium chloride, and an acid, wherein the volumetric ratio of the manganese sulfate and ammonium chloride mixture to the acid is 5:1 to 1:5.

23. The battery of claim 19 , wherein the manganese dioxide is mixed with carbon.

24. The battery of claim 23 , wherein the mix of manganese dioxide and carbon further comprises cobalt oxide, cobalt hydroxide, lead oxide, lead hydroxide, or a combination thereof.

25. The battery of claim 1 , wherein the polymerized catholyte solution comprises potassium permanganate, sodium permanganate, lithium permanganate, calcium permanganate, manganese sulfate, manganese chloride, manganese nitrate, manganese perchlorate, manganese acetate, manganese triflate, manganese carbonate, manganese oxalate, manganese fluorosilicate, manganese ferrocyanide, manganese bromide, magnesium sulfate, ammonium chloride, ammonium sulfate, ammonium hydroxide, zinc sulfate, zinc triflate, zinc acetate, zinc nitrate, bismuth chloride, bismuth nitrate, nitric acid, sulfuric acid, hydrochloric acid, sodium sulfate, 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 nitrite, lithium hydroxide, lithium perchlorate, lithium oxalate, lithium fluoride, lithium carbonate, lithium sulfate, lithium bromate, polyvinyl alcohol, carboxymethyl cellulose, xanthum gum, carrageenan, acrylamide, potassium persulfate, sodium persulfate, ammonium persulfate, N,N′-Methylenebisacrylamide, or a combination thereof.

26. The battery of claim 1 , wherein the polymerized catholyte solution comprises lead sulfate and ammonium chloride at a concentration between 0 and 10M.

27. The battery of claim 1 , wherein the polymerized catholyte solution comprises lead sulfate, ammonium chloride, and an acid, wherein a molar ratio of the lead sulfate and ammonium chloride mixture to the acid is 0.1:5 to 5:0.1.

28. The battery of claim 1 , wherein the cathode further comprises carbon mixed with the lead oxide (PbO 2 ).

29. The battery of claim 28 , where the lead oxide (PbO 2 ) is between 1 and 99 wt. %, and the carbon is between 1 and 99 wt. %.

30. The battery of claim 1 , wherein the polymerized anolyte solution has a pH between 7 and 15.13.

31. The battery of claim 8 , wherein the salt of permanganate comprises potassium permanganate.

32. The battery of claim 10 , wherein the salt of permanganate comprises potassium permanganate.

33. The battery of claim 19 , wherein the polymerized catholyte solution comprises the salt of permanganate, comprising potassium permanganate.

34. The battery of claim 21 , wherein the salt of permanganate comprises potassium permanganate.

35. A high voltage aqueous battery comprising:

a cathode comprising a manganese dioxide, a spinel manganese oxide (Mn 3 O 4 ), or a manganese oxide (MnO);

an anode comprising zinc, aluminum, magnesium, or iron;

a polymerized catholyte solution in contact with the cathode; and

a polymerized anolyte solution in contact with the anode,

wherein the polymerized catholyte solution comprises manganese sulfate, ammonium chloride, and an acid, wherein the volumetric ratio of the manganese sulfate and ammonium chloride mixture to the acid is 5:1 to 1:5.

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