Metal-free high-voltage battery

Abstract

The high-voltage metal-free battery includes a cathode including a cathode electroactive material including at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; an anode including an anode electroactive material including at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; a catholyte in contact with the cathode but not in contact with the anode; and an anolyte in contact with the anode but not in contact with the cathode. The catholyte has a pH less than 4, and the anolyte has a pH greater than 10. The battery includes a separator having ion-selective properties.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 009,278, filed April 13, 2020, entitled "Metal-Free High Voltage Battery," the entire disclosure of which is incorporated herein by reference for all purposes.

[0002] STATEMENT OF GOVERNMENT-SPONSORED RESEARCH OR DEVELOPMENT

[0002] None. [Background technology]

[0003]

[0003] Energy storage systems such as batteries are becoming increasingly important in modern society. As countries transition to greener economies, combining renewable energy sources with energy storage systems is becoming the norm. Batteries are not only used in grid storage applications, but are also increasingly being used in many personal electronic devices and electric vehicles. As the size (physical and capacity (Ah)) of batteries changes depending on the application and market (e.g., grid, electric vehicle, etc.), the closer relationship between batteries and consumers (e.g., personal electronic devices, electric vehicle, etc.) also changes the need for safer, non-toxic, and non-flammable batteries.

[0004] Metal-containing batteries are ubiquitous and have long dominated the battery field, serving several applications for over a century. Some notable examples are zinc, lead, and lithium anode batteries. Silver is used as the cathode. Aluminum and magnesium are gaining momentum as future battery anode materials, but currently these batteries suffer from very low performance due to their high instability. Metals have typically been used as battery anodes due to their tendency to lose electrons. However, the use of metal electrodes in batteries presents challenges in terms of safety, cost, performance, rechargeability, and long-term viability. Some metals, such as zinc and lead, are relatively stable in aqueous electrolytes. However, aqueous electrolytes for some metal electrodes are not viable because their electrochemical activity exceeds the electrolyte's stability range. For example, metals such as lithium, aluminum, and magnesium are highly reactive and unstable in aqueous electrolytes, leading to the development of organic electrolytes for batteries. However, these organic electrolytes are flammable and moisture-sensitive, making these types of batteries expensive to manufacture. A problem with metal anodes, such as zinc and lead, is their tendency to form gases by splitting water to produce hydrogen and oxygen, which can pose safety issues. Similar problems exist with lithium, aluminum, and magnesium batteries, which require expensive, flammable organic electrolytes and a controlled environment for their safe handling.

[0005]

[0005] With regard to rechargeability, metal electrodes tend to form dendrites during repeated cycling, which can lead to separator penetration and battery short-circuiting. This depends on the current density applied during battery charging, but is nevertheless a problem for all metal anode systems, increasing the likelihood of flammability and explosion. Metal electrodes also tend to become passivated by forming oxides or resistive coatings during cycling, which can lead to capacity loss and eventual battery failure. Other problems include metal corrosion and pitting, which hinder long-term rechargeability. There is a continuing need for batteries that are safe, non-flammable, and non-toxic, while exhibiting a relatively wide operating potential window. Summary of the Invention

[0006] In some embodiments, a high voltage metal-free battery includes a cathode including a cathode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; an anode including an anode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; and a conductive layer not in contact with the anode but in contact with the cathode. Positive electrolyte and not in contact with the cathode but in contact with the anode. Negative electrolyte and, Negative electrolyte and Positive electrolyte and a separator disposed between the Positive electrolyte The pH of the solution is less than 4. Negative electrolyte The pH of the separator is above 10. The separator has ion-selective properties.

[0007] In some embodiments, a method of forming a high voltage metal-free battery includes contacting a cathode comprising a cathode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof. Positive electrolyte in contact with an anode comprising an anode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof. Negative electrolyteand not in contact with the cathode Negative electrolyte and not in contact with the anode Positive electrolyte and disposing a separator between the Positive electrolyte The pH of the solution is less than 4. Negative electrolyte The pH of the separator is above 10. The separator has ion-selective properties.

[0008]

[0008] These and other features will be more clearly understood from the following detailed description taken in conjunction with the accompanying claims. [Brief explanation of the drawings]

[0009]

[0009] For a more complete understanding of the present disclosure and its advantages, reference is now made to the following brief description, taken in conjunction with the accompanying drawings and detailed description, in which like reference numerals indicate like parts.

[0010] [Figure 1A]

[0010] FIG. 1 shows a schematic diagram of a high voltage metal-free battery according to some embodiments. [Figure 1B]

[0010] FIG. 1 shows a schematic diagram of a high voltage metal-free battery according to some embodiments. [Figure 1C]

[0010] FIG. 1 shows a schematic diagram of a high voltage metal-free battery according to some embodiments. [Figure 1D]

[0010] FIG. 1 shows a schematic diagram of a high voltage metal-free battery according to some embodiments. [Figure 2]

[0011] 1 shows a graph of voltage over time for a high voltage metal-free battery. [Figure 3]

[0012] Figure 1 shows the discharge curves of a high voltage metal-free battery compared to a MnO2|Zn battery. [Figure 4]

[0013] 1 shows the discharge capacity curve of a high voltage metal-free battery. [Figure 5]

[0014] 1 shows the discharge capacity curve of a high voltage metal-free battery. DETAILED DESCRIPTION OF THE INVENTION

[0011]

[0015] In this disclosure, the terms "negative electrode" and "anode" are both used to mean "negative electrode." Similarly, the terms "positive electrode" and "cathode" are both used to mean "positive electrode." Reference to "electrode" alone can refer to the anode, the 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 is disposed of and replaced after a single discharge. The term "secondary battery" (e.g., "secondary battery," "secondary electrochemical cell," or "secondary cell") refers to a cell or battery that can be recharged one or more times and reused. As used herein, " Positive electrolyte " refers to the electrolyte that is in contact with the cathode without being in direct contact with the anode, Negative electrolyte " refers to the electrolyte that is in contact with the anode but not in direct contact with the cathode. Positive electrolyte , Negative electrolyte or the electrolyte in direct contact with both the anode and cathode.

[0012]

[0016] As used herein, the term "metal-free battery" refers to a battery formed without the use of metallic electroactive materials or metal electrodes (i.e., elemental metal electrodes or alloy metal electrodes), including metal-free electrodes (e.g., metal-free electrodes may include oxides, hydroxides, sulfides, and salts of other metals). Metal-free batteries are also referred to as metal-free electrode batteries, in which the electroactive components of the electrodes do not include elemental or alloy metals, even if another non-electroactive component (part of the reaction that produces the current), such as the current collector, includes elemental or alloy metals. Furthermore, as used herein, the term "metal-free electrode" refers to an electrode formed from and including a material other than a metal with an oxidation state of 0. For example, Zn 0(Zn, which has an oxidation state of 0) may not be a suitable material for forming an electrode in the metal-free battery disclosed herein. However, metals with oxidation states other than 0 may be part of the metal-free electrodes and metal-free batteries disclosed herein, and in some embodiments, a metal-free electrode may be paired with a metal electrode. Another example is Mn 4+ (Mn with an oxidation state of +4) is a suitable material for forming electrodes in the metal-free batteries disclosed herein; for example, MnO2 may be used as the cathode material.

[0013]

[0017] Energy storage systems such as batteries are useful in a variety of applications, such as grid-based, electric vehicles, solar storage, uninterruptible power supplies, etc. Metal-containing batteries are ubiquitous and have long dominated the battery field. However, the use of metal electrodes in batteries presents challenges in terms of safety, cost, performance, rechargeability, and long-term viability.

[0014]

[0018] The development of metal-free batteries would solve some of the problems present in metal-based batteries. However, the battery's voltage, or potential, depends on both the cathode and anode, as well as the anode's ability to lose electrons, which is suitable for metal-based electrodes. In a single electrolyte system, different metal oxides or sulfides, such as manganese dioxide (MnO), hausmannite (MnO), nickel hydroxide [Ni(OH)], nickel oxyhydroxide (NiOOH), and others, cannot be paired because they tend to accept electrons and behave more like cathodes. Furthermore, the voltage generated between these promising electrode active materials is negligible.

[0015]

[0019] In this disclosure, a metal-free dual electrolyte battery is disclosed that has relatively high voltage, relatively high capacity, and can be recharged when necessary. Non-limiting examples of battery chemistries suitable for use in this disclosure in metal-free batteries include manganese dioxide (MnO2)|manganese dioxide (MnO2), MnO2|bixbite (Mn2O3), MnO2|hausmannite (Mn3O4), MnO2|manganese oxide (MnO), MnO2|pyrochlorite [Mn(OH)2], MnO2|manganese oxyhydroxide (MnOOH), MnO2|nickel oxyhydroxide (NiOOH), MnO2|nickel hydroxide [Ni(OH)2], MnO2| Examples of suitable electrolytes include iron oxide (Fe2O3), MnO2|iron oxide (Fe3O4), MnO2|copper oxide (Cu2O, CuO), MnO2|copper hydroxide [Cu(OH)2], MnO2|cobalt oxide (Co3O4), NiOOH|NiOOH, NiOOH|Ni(OH)2, nickel oxide (Ni2O3)|NiOOH, Ni2O3|Ni(OH)2, nickel oxide (NiO)|NiOOH, NiO|Ni(OH)2, nickel oxide (Ni2O3, NiO)|copper oxide (CuO, Cu2O), or any combination thereof. The anode and cathode in these systems are interchangeable. The use of dual electrolytes, with a high proton activity such as an acid and a high hydroxyl activity such as a base, may enable these systems to generate operating voltages. For example, a combination of MnO2|MnO2 and a concentrated acid ( Positive electrolyte ) and base ( Negative electrolyte ) can produce potentials in excess of about 2 V. As an example, disclosed herein is the chemistry of a single redox active element (Mn) whose oxide is paired in a high voltage aqueous battery that can outperform conventional alkaline MnO2 / zinc (Zn) batteries in terms of energy (voltage x capacity) and rechargeability.

[0016]

[0020] In this disclosure, manganese dioxide (MnO2)|manganese dioxide (MnO2), MnO2|bixbite (Mn2O3), MnO2|hausmannite (Mn3O4), MnO2|pyrochlorite [Mn(OH)2], MnO2|manganese oxyhydroxide (MnOOH), MnO2|nickel oxyhydroxide (NiOOH), MnO2|nickel hydroxide [Ni(OH)2], MnO2|iron oxide (Fe2O3), MnO2|iron oxide (Fe3O4), MnO2|copper oxide (Cu2O, CuO), MnO2|copper hydroxide [Cu(OH)2], MnO2|cobalt oxide (Co3O4), NiOOH|N By employing a new battery chemistry that may include nickel oxide (NiOOH), NiOOH|Ni(OH), nickel oxide (NiO)|NiOOH, NiO|Ni(OH), nickel oxide (NiO)|NiOOH, NiO|Ni(OH), nickel oxide (NiO, NiO)|copper oxide (CuO, CuO)), or any combination thereof, and a dual electrolyte, a method is disclosed for creating a metal-free battery with a dual electrolyte, where one electrode is in an electrolyte with high proton activity (e.g., acid) and the other electrode is in an electrolyte with high hydroxyl activity (e.g., base). For example, if the battery is based on a chemistry such as MnO|NiOOH, either electrode can be in acid or base, so all of the above chemistry systems (e.g., the new battery chemistry) can function like a cathode and anode with positive voltages according to standard electrochemical reactions in the respective media (e.g., standard electrochemical reactions in acidic media, standard electrochemical reactions in basic media). This separation or decoupling of electrolytes of different activity, several new battery chemistries previously unsuitable for practical use in batteries, are disclosed herein. The new battery chemistries disclosed herein advantageously open up the fabrication of batteries in which a single redox-active element operates through conversion reactions in a dual electrolyte system. The electrode pairs (e.g., new battery chemistries) disclosed herein have not previously been attempted or reported in the patent or academic literature.

[0017]

[0021] In this disclosure, metal-free batteries may be based on a single redox-active element (manganese), whose oxides may be paired together as the cathode and anode to produce a high-voltage aqueous battery. In some embodiments, the metal-free batteries disclosed herein may outperform conventional alkaline MnO2|Zn batteries in terms of voltage, capacity, and rechargeability. Non-limiting examples of electrode systems of single redox-active manganese elements and their oxides suitable for use in this disclosure include MnO2|MnO2 and / or MnO2|Mn3O4. Further non-limiting examples of electrode systems suitable for use in this disclosure include the new battery chemistries disclosed herein based on single redox-active elements other than Mn (e.g., Ni, Fe, Cu, Ag, etc.) and / or their organic compounds, oxides, hydroxides, oxyhydroxides, and / or sulfides.

[0018]

[0022] In some embodiments, electrode electroactive materials (e.g., anode electroactive materials, cathode electroactive materials) suitable for use in electrodes of the high-voltage metal-free batteries disclosed herein can include manganese dioxide (MnO), which can be any polymorph that occurs in nature or can be created in the laboratory. Non-limiting examples of MnO suitable for use in the metal-free electrodes disclosed herein include electrolytic manganese dioxide (EMD), α-MnO, β-MnO, γ-MnO, δ-MnO, ε-MnO, λ-MnO, or any combination thereof. Other forms of MnO may also be present in the metal-free electrodes disclosed herein, such as pyrolusite, birnessite, bismuth-birnessite, copper-intercalated bismuth birnessite, copper-intercalated birnessite, ramsdellite, hollandite, romanekite, todorokite, lithiophorite, chalcophanite, sodium- or potassium-enriched birnessite, cryptomelane, buserite, partially or fully protonated manganese dioxide, lithiated manganese dioxide, and the like, or any combination thereof. As disclosed herein, "manganese dioxide (MnO)" is understood to encompass any suitable polymorph, which may be naturally occurring or created in the laboratory, as well as any mixed oxide and / or mineral containing manganese dioxide, such as EMD, α-MnO, β-MnO, γ-MnO, δ-MnO, ε-MnO, λ-MnO, pyrolusite, birnessite, bismuth-birnessite, copper-intercalated bismuth-birnessite, copper-intercalated birnessite, ramsdellite, hollandite, romanekite, todorokite, lithiophorite, chalcophanite, sodium- or potassium-enriched birnessite, cryptomelane, buserite, partially or fully protonated manganese dioxide, lithiated manganese dioxide, etc., or any combination thereof. Without wishing to be bound by theory, the mechanism by which batteries such as MnO2|MnO2 work is through solid-state proton insertion and dissolution-precipitation reactions in both acid and basic electrolytes.While MnO2 in acidic media tends to form electrolytic manganese dioxide, or γ-MnO2, upon charging through a one- or two-electron reaction, MnO2 in basic electrolytes converts itself to δ-MnO2 upon charging after a sequential one- or two-electron reaction. γ-MnO2 undergoes solid-state proton insertion for its first electron reaction and a dissolution-precipitation reaction for its second electron reaction in both media, while γ-MnO2 in basic electrolytes ultimately converts to δ-MnO2. γ-MnO2 in acidic media can also undergo a direct dissolution-precipitation reaction, depending on the strength of the acid used. Therefore, batteries of γ-MnO2|γ-MnO2 and γ-MnO2|δ-MnO2 can be created to operate through a wide range of chemical reactions. A γ-MnO2|Mn3O4 battery may have γ-MnO2 operating in an alkaline electrolyte but in an acidic electrolyte, and operation of the battery may involve exchanging the electrolytes, e.g., γ-MnO2 in base and Mn3O4 in acid. In the case of γ-MnO2 in acid, proton insertion and dissolution precipitation or dissolution precipitation follow, depending on the strength of the acid, while Mn3O4 follows a direct dissolution precipitation reaction.

[0019]

[0023] The rechargeable characteristics of the metal-free batteries disclosed herein can be achieved by adding dopants or additives to the electrodes and / or electrolyte. In some embodiments, electrode additives can help enhance the rechargeability of the metal-free batteries disclosed herein. Regardless of the electroactive redox elements (e.g., Mn, Ni, Cu, Fe, Ag, etc.) and their compounds (e.g., oxides, hydroxides, oxyhydroxides, sulfides, organic compounds) used in the metal-free batteries, the electrode additives disclosed herein can be used in both the cathode and anode materials. Non-limiting examples of electrode additives suitable for use in the metal-free electrodes disclosed herein include bismuth oxide, indium oxide, indium hydroxide, copper oxide, aluminum oxide, lead oxide, lead sulfide, bismuth sulfide, silver oxide, nickel oxide, nickel hydroxide, cobalt oxide, or any combination thereof.

[0020]

[0024] Separating electrolytes at different pH levels can be important to prevent neutralization reactions. In some embodiments, electrolyte separation can be achieved by electrolyte gelation, which physically prevents electrolyte mixing. The use of crosslinkers and ionomers in the gelation process can also prevent ionic crossover, allowing for the use of cellulosic separators such as cellophane or polymeric separators such as polyvinyl alcohol or crosslinked polyvinyl alcohol. The electrolyte gelation process can be carried out using a free radical polymerization process. Acrylamide and acrylic acid can be mixed with electrolytes with high proton activity or high hydroxyl activity to form long polymer chains. Crosslinkers such as N,N'-methylenebisacrylamide (MBA) can be used to increase the strength, viscosity, and self-healing properties of the polymer. Electrolyte gelation or polymerization can be carried out using initiators such as potassium persulfate, sodium persulfate, or ammonium persulfate. In some embodiments, preventing electrolyte mixing can be achieved by using an ion-selective ceramic separator or membrane, such as LiSiCON, NaSiCON, Nafion membrane, anion exchange membrane, bipolar membrane, or any combination thereof.

[0021]

[0025] Cathode side Positive electrolyte The proton activity is relatively high at the anode side. Negative electrolyte The advantage of having a dual electrolyte cell with relatively high hydroxyl activity is increased cell potential. Higher proton activity on the cathode side and relatively high hydroxyl activity on the anode side can increase the cell potential, which in turn can lead to a higher average discharge voltage and more energy from the cell.

[0022]

[0026] Another advantage of separating the electrolytes used for the cathode and anode is the generation of positive voltage and cyclability for the novel battery chemistries disclosed herein. Generally, acids are preferred for the cathode and bases for the anode. Electrolytes may be interchangeable between the cathode and anode. Non-limiting examples of acids suitable for use in the metal-free batteries of the present disclosure include hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, hydroiodic acid, triflic acid, or any combination thereof. Non-limiting examples of bases suitable for use in the metal-free batteries of the present disclosure include ammonia, methylamine, glycine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, or any combination thereof.

[0023]

[0027] In some embodiments, electrolyte additives can help improve battery performance. Non-limiting examples of electrolyte additives suitable for use in the metal-free batteries of the present disclosure include manganese sulfate, nickel sulfate, potassium permanganate, manganese chloride, manganese acetate, manganese triflate, bismuth chloride, bismuth nitrate, manganese nitrate, nickel sulfate, nickel nitrate, zinc sulfate, zinc chloride, zinc acetate, zinc triflate, indium chloride, copper sulfate, copper chloride, lead sulfate, sodium persulfate, potassium persulfate, ammonium persulfate, ammonium chloride, vanillin, sodium hypophosphate, potassium chloride, sodium chloride, or any combination thereof.

[0024]

[0028] In some embodiments, electrolytes can be gelled with a suitable additive, which helps physically separate the electrolytes and prevent neutralization of the electrolyte. The gelling or polymerization of the electrolyte can be achieved by various techniques, such as via free radical polymerization. Acrylamide and acrylic acid can be mixed with electrolytes with relatively high proton activity or relatively high hydroxyl activity to form long polymer chains. Crosslinkers such as MBA can be used to increase the strength of the polymer, make it more viscous, and impart self-healing properties to the polymer. The gelling or polymerization can be achieved using an initiator such as potassium persulfate, sodium persulfate, or ammonium persulfate.

[0025]

[0029] Electrolyte separation can be achieved by using any suitable methodology. For example, a gel layer embedded with an ionomer having ion-selective properties can act as a barrier layer to prevent the crossover of neutralizing ions. The gelation procedure can be carried out via free radical polymerization as disclosed herein. Buffer additives, which may include potassium sulfate, sodium sulfate, potassium bicarbonate, sodium bicarbonate, etc., or any combination thereof, can be added to the gelled ionomer. Ion-selective ceramic separators or membranes, such as LiSiCON, NaSiCON, Nafion membranes, anion exchange membranes, bipolar membranes, etc., can also be used to achieve electrolyte separation.

[0026]

[0030] Disclosed herein is a high-voltage metal-free battery that utilizes dual electrolytes to generate high voltage and capacity for the corresponding electrodes. For the first time, a novel electrode pair is presented that advantageously exhibits the additional battery benefits of safety, non-toxicity, and non-flammability. For the first time in the patent and academic literature, a single redox-active element pair is disclosed, and this novel electrode chemistry pair exhibits the conversion properties of dual electrolytes that advantageously increase the battery's energy density.

[0027]

[0031] Disclosed herein is a high voltage metal-free battery capable of delivering an average discharge capacity between greater than 1.6V and 5V over an operating range between 0V and 5V, with both single use and rechargeable characteristics.

[0028]

[0032] In this disclosure, a metal-free high-voltage aqueous battery is disclosed. In this disclosure, the high-voltage metal-free battery may be characterized by an average discharge potential between greater than 1.6 V and 5 V. The average discharge potential of a conventional alkaline MnO2|Zn battery is 1.6 V. The high-voltage metal-free battery disclosed herein may have single-discharge or rechargeable characteristics, depending on the use of dopants or additives in the electrodes or electrolyte. The high-voltage metal-free battery disclosed herein may be single-use or rechargeable. The electrode pair in this system may be an oxide, hydroxide, oxyhydroxide, sulfide, organic compound, or any combination thereof, of a single redox-active element, and / or a pair of various oxides, hydroxides, oxyhydroxides, sulfides, or any combination thereof that retain the structure of an oxide, hydroxide, oxyhydroxide, sulfide, organic compound, or any combination thereof during charging and discharging, respectively. Without wishing to be bound by theory, the resulting capacity may be due to ion insertion or intercalation and / or dissolution-precipitation mechanisms. Relatively high discharge potentials may be achieved by separating electrolytes with different strengths in terms of hydrogen (or proton) activity and hydroxyl activity. In some embodiments, long-term rechargeability of high-voltage metal-free batteries may be achieved through the use of additives and / or dopants. Negative electrolyte and Positive electrolyte Separation can also be achieved through the use of ion-selective ceramic and / or polymer membranes. In some cases, separation can be achieved through the use of gelling electrolytes with embedded ion-selective ionomers to prevent neutralization by ion migration. Additionally, gelling separators that function as buffer layers containing ion-selective ionomers and buffering agents can be used to Negative electrolyte of Positive electrolyteNon-limiting examples of buffering agents suitable for use in the buffer layer of the present disclosure include potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, or any combination thereof.

[0029]

[0033] In this disclosure, high-voltage metal-free batteries can be of any geometric form factor as desired. To those skilled in the art, high-voltage aqueous Zn anode batteries can be cylindrical or prismatic. Furthermore, high-voltage metal-free batteries can also be flexible as desired by gelling the electrolyte and electrodes or by using binders in the electrodes that allow flexibility.

[0030]

[0034] 1A-1D , 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 include an anode current collector 4 and an anode material 5. Note that the scale of the components in FIGS. 1A-1D may not be accurate because the features are drawn to clearly show the electrolyte surrounding the anode 13 and cathode 12. FIGS. 1A-1C show a prismatic battery configuration with a single anode 13 and cathode 12. In another embodiment, the battery can be a cylindrical battery (e.g., as shown in FIG. 1D ) with concentrically arranged electrodes or in a rolled configuration in which the anode and cathode are layered and then rolled to form a jellyroll configuration. The cathode current collector 1 and cathode material 2 are collectively referred to as the cathode 12 or positive electrode 12, as shown in FIG. 1D . Similarly, the anode material 5 with optional anode current collector 4 may be collectively referred to as anode 13 or negative electrode 13. An electrolyte may be in contact with cathode 12 and anode 13. As described in more detail herein, the electrolyte in contact with both cathode 12 and anode 13 may be substantially the same, with different concentrations of protons and hydroxyl ions, or different electrolyte compositions may be used with anode 13 and cathode 12 to modify the properties of battery 10 in some embodiments.

[0031]

[0035] In some embodiments, battery 10 may include one or more cathodes 12 and one or more anodes 13, which may be present in any configuration or form factor. When multiple anodes 13 and / or multiple cathodes 12 are present, the electrodes may be arranged in a layered configuration, with the electrodes alternating (e.g., anode, cathode, anode, etc.). Any number of anodes 13 and / or cathodes 12 may be present to provide a desired capacity and / or output voltage. In a jelly-roll configuration (e.g., as shown in FIG. 1D ), multiple cathodes 12 and anodes 13 may be used in a layered configuration or may be rolled to form a rolled configuration with alternating layers, although battery 10 may have only one cathode 12 and one anode 13 in a rolled configuration such that a cross-section of battery 10 includes a layered configuration of alternating electrodes.

[0032]

[0036] In one embodiment, housing 7 comprises a molded box or container that contains the electrolyte and is generally non-reactive with the electrolyte solution in battery 10. In one embodiment, housing 7 comprises a polymer (e.g., a molded polypropylene box, an acrylic polymer molded box, etc.), a coated metal, or the like.

[0033]

[0037] Cathode 12 may include a mixture of components including an electrochemically active material (e.g., a cathode electroactive material). Anode 13 may include a mixture of components including an electrochemically active material (e.g., an anode electroactive material). As disclosed herein, a metal-free battery may have a metal-free cathode electroactive material and a metal-free anode electroactive material, although metals may be present in other portions of the battery. Additional components, such as binders, conductive materials, and / or one or more additional components, may optionally be included that may help improve the life, rechargeability, and electrochemical properties of the metal-free electrodes (e.g., cathode 12, anode 13). Cathode 12 may include cathode material 2 (e.g., electroactive material, additives, etc.). Cathode 12 may include between about 1% and about 95% active material by weight. Anode 13 may include anode material 5 (e.g., electroactive material, additives, etc.). Anode 13 can include between about 1% and about 95% active material by weight.

[0034]

[0038] The high-voltage metal-free battery disclosed herein includes metal-free electrodes, such as a metal-free cathode 12 and a metal-free anode 13. In some embodiments, the electroactive material of each electrode may be metal-free, even if metal is present in the electrode or other portions of the battery. The cathode 12 and anode 13 pair may be any combination of the electrode materials disclosed herein, which may exist as organic compounds, oxides, hydroxides, oxyhydroxides, and / or sulfides.

[0035]

[0039] Suitable electrode materials (e.g., cathode material 2, anode material 5) include manganese dioxide, copper manganese oxide, hausmannite, manganese oxide, copper intercalated bismuth birnessite, birnessite, todorokite, ramsdellite, pyrolusite, pyrochlorite, silver compounds, silver oxide, silver dioxide, nickel compounds, nickel organic compounds, nickel oxyhydroxide, nickel hydroxide, lead oxide, copper oxide, copper dioxide, lead compounds, lead dioxide (alpha and beta), potassium persulfate, sodium persulfate, ammonium persulfate, potassium permanganate, calcium permanganate, barium permanganate, silver permanganate, ammonium permanganate, peroxides, gold compounds, perchlorates, cobalt oxides (CoO, CoO2, Co3O4), lithium cobalt oxide, sodium cobalt oxide, perchlorates, nickel oxide Examples of suitable cathodes include, but are not limited to, MnO, heterolite (ZnMnO), barium hydroxide, aluminum hydroxide, bromine, mercury compounds, vanadium oxide, bismuth vanadium oxide, hydroquinone, calix[4]quinone, tetrachlorobenzoquinone, 1,4-naphthoquinone, 9,10-anthraquinone, 1,2-naphthaquinone, 9,10-phenanthrenequinone, a nitroxide-oxoammonium cation redox couple such as 2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), carbon, 2,3-dicyano-5,6-dichlorodicyanoquinone, tetracyanoethylene, sulfur trioxide, ozone, oxygen, air, lithium nickel manganese cobalt oxide, sulfur, lithium iron phosphate, lithium copper oxide, lithium copper oxyphosphate, or any combination thereof. In some embodiments, the cathode may comprise an air electrode.

[0036]

[0040] In some embodiments, the electrode materials (e.g., cathode material 2, anode material 5) may be based on one or many polymorphs of MnO, including electrolytic manganese dioxide (EMD), α-MnO, β-MnO, γ-MnO, δ-MnO, ε-MnO, or λ-MnO. Other forms of MnO may also be present, such as hydrated MnO, pyrolusite, birnessite, ramsdellite, hollandite, romanekite, todorokite, lithiophorite, chalcophanite, sodium- or potassium-enriched birnessite, cryptomelane, buserite, manganese oxyhydroxide (MnOOH), α-MnOOH, γ-MnOOH, β-MnOOH, manganese hydroxide [Mn(OH)], partially or fully protonated manganese dioxide, MnO, MnO, bixbite, MnO, lithiated manganese dioxide (LiMnO, LiMnO), CuMnO, aluminum manganese oxide, zinc manganese dioxide, bismuth manganese oxide, copper-intercalated birnessite, copper-intercalated bismuth birnessite, tin-doped manganese oxide, magnesium manganese oxide, or any combination thereof. Generally, the cycling form of manganese dioxide in the electrode may have a layered structure, which in some embodiments may include δ-MnO2, which is interchangeably referred to as birnessite. When non-birnessite polymorphic forms of manganese dioxide are used, they may be converted to birnessite in situ by one or more conditioning cycles, which are described in more detail below. For example, a full or partial discharge to the end of the second electron stage of MnO2 (e.g., between about 20% and about 100% of the second electron capacity of the cathode) may be performed, followed by the recharging of the MnO2. 4+ state, resulting in birnessite phase manganese dioxide.

[0037]

[0041] In some embodiments, electrode materials (e.g., cathode material 2, anode material 5) suitable for use in the high-voltage metal-free batteries disclosed herein may include electrolytic manganese dioxide (EMD), α-MnO2, β-MnO2, γ-MnO2, δ-MnO2, ε-MnO2, λ-MnO2, or any combination thereof. Other forms of MnO may also be present in the electrode material, such as pyrolusite, birnessite, ramsdellite, hollandite, romanekite, todorokite, lithiophorite, chalcophanite, sodium- or potassium-enriched birnessite, cryptomelane, buserite, manganese oxyhydroxide (MnOOH), α-MnOOH, γ-MnOOH, β-MnOOH, manganese hydroxide [Mn(OH)2], partially or fully protonated manganese dioxide, Mn3O4, Mn2O3, bixbite, MnO, lithiated manganese dioxide (LiMn2O4), CuMn2O4, zinc manganese dioxide, or any combination thereof.Non-limiting examples of electrode materials (e.g., cathode material 2, anode material 5) suitable for use in the high voltage metal-free batteries disclosed herein include electrolytic manganese dioxide (EMD), α-MnO2, β-MnO2, γ-MnO2, δ-MnO2, ε-MnO2, λ-MnO2, pyrolusite, birnessite, ramsdellite, hollandite, romanekite, todorokite, lithiophorite, chalcophanite, sodium- or potassium-enriched birnessite, cryptomelane, buserite, manganese oxyhydroxide (MnOOH), α-MnOOH, γ-MnOOH, β-MnOOH, manganese hydroxide [Mn(OH)2], partially or fully protonated manganese dioxide, Mn3O4, Mn2O3, bixbite, MnO, lithiated manganese dioxide (LiMn2O4 ), CuMn2O4, zinc manganese dioxide, lead oxide, lead dioxide, copper oxide, copper hydroxide, silver oxide, nickel oxide, nickel hydroxide, nickel oxyhydroxide, cobalt oxide, cobalt hydroxide, lithium nickel manganese cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium cobalt oxide, lithium iron phosphate, potassium iron oxide, barium iron oxide, copper hexacyanoferrate, delithiated manganese oxide, delithiated nickel oxide, delithiated nickel manganese oxide, delithiated nickel manganese cobalt oxide, iron oxide, iron hydroxide, tin oxide, tin sulfide, manganese sulfide, nickel sulfide, copper sulfide, tungsten oxide, tungsten disulfide, calix[4]quinone, 1,4-naphthoquinone, 9,10-anthraquinone, vanadium oxide, or any combination thereof.

[0038]

[0042] The cells described herein may comprise any of the cathode materials described herein, in combination with a suitable electrolyte (e.g., a suitable Negative electrolyte and Positive electrolyte With any of the anode materials described to the extent that they are capable of generating a voltage in the presence of

[0039]

[0043] In some embodiments, the cathode 12 used in the high voltage metal-free batteries disclosed herein is made of a metal-free metal, such as a metal oxide, a metal hydroxide, a metal oxyhydroxide, a metal salt (e.g., a metal sulfide), an organic compound, or the like. Positive electrolyte The electrolyte may include an electroactive material that is electrochemically active in an electrolyte with high proton activity, such as 3.

[0040]

[0044] In some embodiments, the anode 13 used in the high voltage metal-free batteries disclosed herein can be made of a metal-free metal, such as a metal oxide, a metal hydroxide, a metal oxyhydroxide, a metal salt (e.g., a metal sulfide), an organic compound, or the like. Negative electrolyte The present invention may include electroactive materials that are electrochemically active in electrolytes with high hydroxyl activity, such as in 6.

[0041]

[0045] Non-limiting examples of electrode materials (e.g., cathode material 2, anode material 5) that are electrochemically active in high proton activity or high hydroxyl activity electrolytes include electrolytic manganese dioxide (EMD), α-MnO2, β-MnO2, γ-MnO2, δ-MnO2, ε-MnO2, λ-MnO2, or any combination thereof. Other forms of MnO2 include pyrolusite, birnessite, ramsdellite, hollandite, romanekite, todorokite, lithiophorite, chalcophanite, sodium-rich birnessite, potassium-rich birnessite, cryptomelane, buserite, manganese oxyhydroxide (MnOOH), α-MnOOH, γ-MnOOH, β-MnOOH, manganese hydroxide [Mn(OH)2], partially or fully protonated manganese dioxide, Mn3O4, Mn2O3, bixbite, MnO, lithiated manganese dioxide (LiMn2O4), CuMn2O4, zinc manganese dioxide, lead oxide, lead dioxide, copper compounds, copper oxide, copper hydroxide, silver compounds, silver oxide. Nickel compounds, nickel oxide, nickel hydroxide, nickel oxyhydroxide, cobalt oxide, cobalt compounds, cobalt hydroxide, lithium nickel manganese cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium cobalt oxide, lithium iron phosphate, potassium iron oxide, barium iron oxide, copper hexacyanoferrate, delithiated manganese oxide, delithiated nickel oxide, delithiated nickel manganese oxide, delithiated nickel manganese cobalt oxide, quinone compounds such as calix[4]quinone, 1,4-naphthoquinone, 9,10-anthraquinone, or any combination thereof, may also be present in the electrodes (e.g., cathode 12, anode 13). Combinations of electroactive materials may also be employed in the electrode materials (e.g., cathode material 2, anode material 5). The electroactive electrode materials (e.g., electroactive cathode material 2, electroactive anode material 5) may be in the form of powders with various particle sizes (nanometers to micrometers).

[0042]

[0046] Examples of battery systems suitable for use in the high voltage metal-free batteries disclosed herein include manganese dioxide (MnO2)|manganese dioxide (MnO2), MnO2|bixbite (Mn2O3), MnO2|hausmannite (Mn3O4), MnO2|pyrochlorite [Mn(OH)2], MnO2|manganese oxyhydroxide (MnOOH), MnO2|manganese oxide (MnO), MnO2|nickel oxyhydroxide (NiOOH), MnO2|nickel hydroxide [Ni(OH)2], MnO2| Examples of suitable oxides include iron oxide (FeO), MnO|iron oxide (FeO), MnO|copper oxide (CuO, CuO), MnO|copper hydroxide [Cu(OH)], MnO|cobalt oxide (CoO), NiOOH|NiOOH, NiOOH|Ni(OH), nickel oxide (NiO)|NiOOH, NiO|Ni(OH), nickel oxide (NiO)|NiOOH, NiO|Ni(OH), nickel oxide (NiO, NiO)|copper oxide (CuO, CuO), or any combination thereof. MnO, NiOOH, etc., when paired in these battery systems, can exist in various polymorphic forms.

[0043]

[0047] The cathode electroactive material and / or the anode electroactive material may need to be mixed with a conductive additive, such as carbon. The addition of a conductive additive, such as conductive carbon, allows for a high loading of the electroactive material in the electrode material (e.g., cathode material 2, anode material 5), resulting in higher volumetric and gravimetric energy densities. In some embodiments, the conductive additive may be present in the electrode material (e.g., cathode material 2, anode material 5) in an amount of about 1 to 30 wt %, based on the total weight of the electrode material (e.g., cathode material 2, anode material 5). In some embodiments, the conductive additive may include graphite, carbon fiber, carbon black, acetylene black, single-walled carbon nanotubes, multi-walled carbon nanotubes, single-walled carbon nanotube dispersions, multi-walled carbon nanotube dispersions, graphene, graphene, graphene oxide, or combinations thereof. Higher loading of the electroactive material in the electrodes (e.g., cathode 12, anode 13) is desirable in some embodiments to increase energy density. Other examples of conductive carbon include TIMREX primary synthetic graphite (all types), TIMREX natural flake graphite (all types), TIMREX MB, MK, MX, KC, B, LB grades (e.g., KS15, KS44, KC44, MB15, MB25, MK15, MK25, MK44, MX15, MX25, BNB90, LB family), TIMREX dispersions; ENASCO 150G, 210G, 250G, 260G, 350G, 150P, 250P; SUPER P, SUPER P Li, carbon black (e.g., Ketjenblack EC-300J, Ketjenblack EC-600JD, Ketjenblack EC-600JD powder), acetylene black, carbon nanotubes (single-walled or multi-walled), Zenyatta graphite, and / or combinations thereof.

[0044]

[0048] In some embodiments, the particle size range of the conductive additive can be about 1 to about 50 microns, or between about 2 microns and about 30 microns, or between about 5 microns and about 15 microns. In one embodiment, the conductive additive can include expanded graphite having a particle size range of about 10 to about 50 microns, or about 20 to about 30 microns. Carbon fibers and nanotubes can have various aspect ratios, with diameters ranging from tens to hundreds of nanometers. In some embodiments, the mass ratio of graphite to conductive additive can be in the range of about 5:1 to about 50:1, or about 7:1 to about 28:1. The total mass fraction of the conductive additive (e.g., the total mass fraction of carbon) in the electrode materials (e.g., cathode material 2, anode material 5) can be in the range of about 5% to about 99%, or about 10% to about 80%. In some embodiments, the electroactive component in the electrode material (e.g., cathode material 2, anode material 5) can be between 1 wt % and 99 wt % of the weight of the electrode material (e.g., cathode material 2, anode material 5), and the conductive additive can be between 1 wt % and 99 wt % of the weight of the electrode material (e.g., cathode material 2, anode material 5).

[0045]

[0049] In some embodiments, dopants or additives can be added to electrode materials (e.g., cathode material 2, anode material 5) to improve rechargeability and performance. The additives can be in the form of a powder mixed with the electroactive material or in the form of a substrate to which electroactive and conductive carbon can be applied. Non-limiting examples of additives suitable for use in electrode materials (e.g., cathode material 2, anode material 5) of the present disclosure include bismuth compounds, bismuth oxide, copper oxide, copper compounds, indium compounds, indium hydroxide, indium oxide, aluminum compounds, aluminum oxide, nickel compounds, nickel hydroxide, nickel oxide, silver compounds, silver oxide, cobalt compounds, cobalt oxide, cobalt hydroxide, lead compounds, lead oxide, lead dioxide, quinones, salts thereof, derivatives thereof, or any combination thereof. In some embodiments, the dopant or additive can be present in the electrode material (e.g., cathode material 2, anode material 5) in an amount between 0 and 30 wt %, based on the total weight of the electrode material (e.g., cathode material 2, anode material 5).

[0046]

[0050] In some embodiments, the electrode material (e.g., cathode material 2, anode material 5) may also include a conductive component. Addition of the conductive component to the electrode material (e.g., cathode material 2, anode material 5) may be achieved by adding a powder of the conductive component to the electrode material (e.g., cathode material 2, anode material 5). The conductive component may be present in the electrode material (e.g., cathode material 2, anode material 5) at a concentration of about 0 to 30% by weight. The conductive component may be, for example, an oxide, salt, and / or hydroxide of one or more metals selected from the group consisting of nickel, copper, silver, gold, tin, cobalt, antimony, brass, bronze, aluminum, calcium, iron, platinum, and any combination thereof. In one embodiment, the conductive component is a powder. In some embodiments, the conductive component may be added as an oxide powder, a salt powder, a hydroxide powder, or a combination thereof. In some embodiments, the conductive component may be cobalt oxide, cobalt hydroxide, lead oxide, lead hydroxide, or a combination thereof. In some embodiments, a second conductive component may be added to act as a supporting conductive framework on which the first and second electronic reactions occur. The second electronic reaction is carried out by Mn 3+ Manganese ions have a dissolution-precipitation reaction in which they dissolve in the electrolyte and precipitate in materials such as graphite, resulting in an electrochemical reaction and the formation of non-conductive manganese hydroxide [Mn(OH)2]. This ultimately leads to capacity loss in subsequent cycles. Suitable conductive components that can help reduce the solubility of manganese ions include oxides, salts, and / or hydroxides of transition metals such as Ni, Co, Fe, and Ti, and / or oxides, salts, and / or hydroxides of metals such as Ag, Au, Al, and Ca. Oxides, salts, and / or hydroxides of transition metals such as Co also contribute to the formation of Mn. 3+This can help reduce the solubility of ions. Such conductive components may be incorporated into electrodes (e.g., cathode 12, anode 13) by chemical or physical means (e.g., ball mill, mortar / pestle, speck mixture). Examples of such electrodes (e.g., cathode 12, anode 13) include 5-95% birnessite, 5-95% conductive carbon, 0-50% conductive component, and 1-10% binder.

[0047]

[0051] In some embodiments, a binder may be used with the electrode materials (e.g., cathode material 2, anode material 5). The binder may be present at a concentration of between about 0 and 10 wt % or between about 1 and 5 wt % of the weight of the electrode materials (e.g., cathode material 2, anode material 5). In some embodiments, the binder may be used as a thickener and strong binder and includes a water-soluble cellulose-based hydrogel crosslinked with a conductive polymer for good mechanical strength. The binder may be a cellulose film sold as cellophane. The binder may be prepared by physically crosslinking a water-soluble cellulose-based hydrogel with a polymer through repeated cooling and thawing cycles. In some embodiments, the binder may include a 0 to 10 wt % carboxymethyl cellulose (CMC) solution crosslinked with 0 to 10 wt % polyvinyl alcohol (PVA) on an equal volume basis. The binder exhibits superior performance compared to traditionally used materials such as TEFLON® or PTFE (polytetrafluoroethylene). Although TEFLON® or PTFE are highly resistive materials, they are widely used in the industry due to their excellent rollability. However, this does not preclude the use of TEFLON® or PTFE as a binder. Mixtures of TEFLON® or PTFE with aqueous binders and some conductive carbon can be used to create rollable binders. The use of aqueous binders can help achieve a significant portion of the two-electron capacity with minimal capacity loss over many cycles. In some embodiments, the binder can be water-based and has excellent water retention and adhesive properties, helping to maintain conductivity compared to an identical cathode using a PTFE binder instead. Examples of suitable water-based hydrogels include, but are not limited to, methyl cellulose (MC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPH), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl methyl cellulose (HEMC), carboxymethyl hydroxyethyl cellulose, hydroxyethyl cellulose (HEC), and combinations thereof.Examples of crosslinked polymers include polyvinyl alcohol, polyvinyl acetate, polyaniline, polyvinylpyrrolidone, polyvinylidene fluoride, polypyrrole, and combinations thereof. In some embodiments, a 0-10 wt% solution of aqueous cellulose hydrogen can be crosslinked with a 0-10 wt% solution of a crosslinked polymer, for example, by repeated freeze / thaw cycles, radiation treatment, and / or chemicals (e.g., epichlorohydrin). The aqueous binder can be mixed with 0-5% PTFE to improve manufacturability.

[0048]

[0052] The electrode materials (e.g., cathode material 2, anode material 5) may also include additional elements. The additional elements may be included in electrode materials (e.g., cathode material 2, anode material 5) that include bismuth compounds and / or copper compounds, which together enable improved constant current battery cycling of the cathode. When present as birnessite, the copper and / or bismuth compounds may be incorporated into the layered nanostructure of the birnessite. The resulting birnessite electrode materials (e.g., cathode material 2, anode material 5) may exhibit improved cycling and long-term performance due to the copper and / or bismuth compounds incorporated into the birnessite crystals and nanostructure.

[0049]

[0053] The bismuth compound may be incorporated into the cathode 12 as an inorganic or organic salt of bismuth (oxidation state 5, 4, 3, 2, or 1) or as bismuth oxide. The bismuth compound may be present in the electrode material (e.g., cathode material 2, anode material 5) at a concentration of between about 1 and 20 weight percent of the weight of the electrode material (e.g., cathode material 2, anode material 5). Examples of bismuth compounds include bismuth chloride, bismuth bromide, bismuth fluoride, bismuth iodide, bismuth sulfate, bismuth nitrate, bismuth trichloride, bismuth citrate, bismuth telluride, bismuth selenide, bismuth subsalicylate, bismuth neodecanoate, bismuth carbonate, bismuth subgallate, bismuth strontium calcium copper oxide, bismuth acetate, bismuth trifluoromethanesulfonate, bismuth nitrate oxide, bismuth gallate hydrate, bismuth phosphate, bismuth cobalt zinc oxide, bismuth sulfite agar, and the like. Examples of suitable bismuth oxides include bismuth oxychloride, bismuth aluminate hydrate, bismuth tungsten oxide, bismuth lead strontium calcium copper oxide, bismuth antimonide, bismuth antimony telluride, yttria-stabilized bismuth oxide (e.g., yttria-doped bismuth oxide), bismuth-lead alloy, bismuth ammonium citrate, 2-naptol bismuth salt, dichloro(tri-o-tolyl)bismuth, dichlorodiphenyl(p-tolyl)bismuth, triphenylbismuth, and / or combinations thereof.

[0050]

[0054] The copper compound may be incorporated into the electrode (e.g., cathode 12, anode 13) as an organic or inorganic salt of copper (oxidation state 1, 2, 3, or 4) or as copper oxide. The copper compound may be present in a concentration of between about 1 and 70 wt. % of the weight of the electrode material (e.g., cathode material 2, anode material 5). In some embodiments, the copper compound is present in a concentration of between about 5 and 50 wt. % of the weight of the electrode material (e.g., cathode material 2, anode material 5). In other embodiments, the copper compound is present in a concentration of between about 10 and 50 wt. % of the weight of the electrode material (e.g., cathode material 2, anode material 5). In still other embodiments, the copper compound is present in a concentration of between about 5 and 20 wt. % of the weight of the electrode material (e.g., cathode material 2, anode material 5). Examples of copper compounds include copper and copper salts such as copper aluminum oxide, copper(I) oxide, copper(II) oxide, and / or copper salts with oxidation states +1, +2, +3, or +4, including, but not limited to, copper nitrate, copper sulfate, copper chloride, etc. The effect of the copper compound is to change the oxidation and reduction voltage of the bismuth compound. This results in electrodes (e.g., cathode 12, anode 13) that have complete reversibility during galvanostatic cycling, compared to bismuth-modified MnO, which cannot even withstand galvanostatic cycling.

[0051]

[0055] The electrodes (e.g., cathode 12, anode 13) can be fabricated using methods that are feasible for large-scale manufacturing. In some embodiments, the electrode material (e.g., cathode material 2, anode material 5) can include 2-30 wt. % conductive carbon, 0-30 wt. % conductive additive, 1-70 wt. % copper compound, 1-20 wt. % bismuth compound, 0-10 wt. % binder, and birnessite or EMD. In another embodiment, the electrode material (e.g., cathode material 2, anode material 5) includes 2-30 wt. % conductive carbon, 0-30 wt. % conductive additive, 1-20 wt. % bismuth compound, 0-10 wt. % binder, and birnessite or EMD. In one embodiment, the electrode materials (e.g., cathode material 2, anode material 5) are primarily composed of 2 to 30% by weight of conductive carbon, 0 to 30% by weight of a conductive additive, 1 to 70% by weight of a copper compound, 1 to 20% by weight of a bismuth compound, 0 to 10% by weight of a binder, and the remainder being birnessite or EMD. In another embodiment, the electrode materials (e.g., cathode material 2, anode material 5) are primarily composed of 2 to 30% by weight of conductive carbon, 0 to 30% by weight of a conductive additive, 1 to 20% by weight of a bismuth compound, 0 to 10% by weight of a binder, and the remainder being birnessite or EMD.

[0052]

[0056] The resulting electrodes (e.g., cathode 12, anode 13) may have a porosity in the range of 20% to 85% as measured by mercury intrusion porosimetry. Porosity may be measured in accordance with ASTM D4284-12, "Standard Test Method for Determining Pore Volume Distribution of Catalysts and Catalyst Supports by Mercury Intrusion Porosimetry," using the version current as of the filing date of this application.

[0053]

[0057] The electrode materials (e.g., cathode material 2, anode material 5) can be formed on electrode current collectors (e.g., cathode current collector 1, anode current collector 4) formed from a conductive material that serves as an electrical connection between the electrode materials (e.g., cathode material 2, anode material 5) and an external electrical connection. As noted herein, the current collectors can be metal in some embodiments. Because the current collectors are not electroactive materials, the battery can be referred to as a metal-free battery even if the current collectors include a metal. In some embodiments, the electrode current collectors (e.g., cathode current collector 1, anode current collector 4) 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, half nickel and half copper, or any combination thereof. In some embodiments, the electrode current collectors (e.g., cathode current collector 1, anode current collector 4) can comprise carbon felt, carbon foam, conductive polymer mesh, or any combination thereof. The electrode current collectors (e.g., cathode current collector 1, anode current collector 4) can be formed into a mesh (e.g., expanded mesh, woven mesh, etc.), perforated metal, foam, foil, felt, fibrous structure, porous block structure, perforated foil, wire screen, packaging assembly, or any combination thereof. In some embodiments, the electrode current collectors (e.g., cathode current collector 1, anode current collector 4) can be formed into or form part of a pocket assembly, in which a pocket can hold electrode material (e.g., cathode material 2, anode material 5) within the electrode current collectors (e.g., cathode current collector 1, anode current collector 4, respectively). Tabs can be coupled to the current collectors to provide electrical connection between an external power source and the current collectors. As shown on top of the electrodes (e.g., cathode 12, anode 13) in FIG. 1B, the tabs can be part of the electrode current collectors (e.g., cathode current collector 1, anode current collector 4) that extend outside the electrode material (e.g., cathode material 2, anode material 5, respectively).

[0054]

[0058] The electrode materials (e.g., cathode material 2, anode material 5) can be pressed against electrode current collectors (e.g., cathode current collector 1, anode current collector 4) to form electrodes (e.g., cathode 12, anode 13, respectively). For example, the electrode materials (e.g., cathode material 2, anode material 5) can be pressed against pressures between, for example, 1,000 psi and 20,000 psi (6.9×10 6 and 1.4 x 10 8 The electrode materials (e.g., cathode material 2 and anode material 5) may be applied to the electrode current collectors (e.g., cathode current collector 1 and anode current collector 4, respectively) by pressing them together with a pressure of between 1000 and 1000 Pascals. The electrode materials (e.g., cathode material 2 and anode material 5) may be applied to the electrode current collectors (e.g., cathode current collector 1 and anode current collector 4, respectively) as a paste. The resulting electrodes (e.g., cathode 12 and anode 13) may have a thickness between about 0.1 mm and about 5 mm.

[0055]

[0059] In some embodiments, the cathode and anode materials with corresponding electroactive materials also contain corresponding electrolytes (e.g., Positive electrolyte and Negative electrolyte The process of forming cathode and anode materials from dissolved salts in the corresponding electrolytes involves a charging or forming step in which the dissolved salt containing the active ions is plated onto a current collector by electrons flowing from an external circuit. For example, manganese salts such as manganese sulfate, manganese triflate, etc., in a highly proton-active electrolyte will electroplate MnO during the charging or forming step.

[0056]

[0060] 1B, battery 10 may not include a separator. The ability to form battery 10 without a separator may allow for a reduction in the overall cost of the battery while having the same or similar performance as a battery with a separator. Positive electrolyte and Negative electrolyte The use of a polymer gel electrolyte (PGE) for the anode 13 and cathode 12 can act as a separator by forming a physical barrier between them to prevent short circuits.

[0057]

[0061] In some embodiments, separator 9 (e.g., as shown in FIGS. 1A and 1C) and / or buffer layer may be disposed between anode 13 and cathode 12 when the electrodes are configured into a battery. Although shown as disposed between anode 13 and cathode 12, separator 9 may be used to encase one or more of anode 13 and / or cathode 12, or one or more of anodes 13 and / or cathodes 12 when multiple anodes 13 and cathodes 12 are present.

[0058]

[0062] The separator 9 may include one or more layers. For example, if a separator is used, 1 to 5 layers of separator may be applied between adjacent electrodes. The separator may be formed from a suitable material, such as nylon, polyester, polyethylene, polypropylene, poly(tetrafluoroethylene) (PTFE), poly(vinyl chloride) (PVC), polyvinyl alcohol, cellulose, or any combination thereof. Suitable layers and separator forms may include, but are not limited to, polymer separator layers such as sintered polymer film membranes, polyolefin membranes, polyolefin nonwoven membranes, cellulose membranes, cellophane, battery-grade cellophane, hydrophilically modified polyolefin membranes, and the like, or combinations thereof. As used herein, the phrase "hydrophilically modified" refers to a material having a contact angle with water of less than 45°. In another embodiment, the material used in the separator has a contact angle with water of less than 30°. In yet another embodiment, the material used in the separator has a contact angle with water of less than 20°. The polyolefin may be modified, for example, by the addition of TRITON X-100™ or oxygen plasma treatment. In some embodiments, separator 9 may include a CELGARD® brand microporous separator. In one embodiment, separator 9 may include an FS 2192 SG membrane, a polyolefin nonwoven membrane commercially available from Freudenberg, Germany. In some embodiments, the separator may include a lithium superionic conductor (LISICON®), a sodium superionic conductor (NASICON®), a NAFION®, a bipolar membrane, a water electrolysis membrane, a composite of polyvinyl alcohol and graphene oxide, polyvinyl alcohol, cross-linked polyvinyl alcohol, or a combination thereof.

[0059]

[0063] Separator 9 can comprise a variety of materials, but if more than one separator is present, the use of a PGE for the electrolyte can allow for the use of a relatively inexpensive separator 9. For example, separator 9 can comprise CELLOPHANE®, polyvinyl alcohol, CELGARD®, a composite of polyvinyl alcohol and graphene oxide, cross-linked polyvinyl alcohol, PELLON®, and / or a carbon-polyvinyl alcohol composite. The use of separator 9 can help improve the cycle life of battery 20, but is not required in all embodiments.

[0060]

[0064] If a buffer layer is used, it may be used alone or in combination with the separator 9. The buffer layer may be Negative electrolyte and / or Positive electrolyte For example, the buffer layer may be a PGE as described herein. One or more additives may also be present in the buffer layer, such as calcium hydroxide, layered double hydroxides such as hydrotalcites, quintinite, vogelite, magnesium hydroxide, or combinations thereof. For example, Negative electrolyte and Positive electrolyte are substantially the same formulation, differing only in proton and hydroxyl anion composition and / or viscosity, the electrolyte concentration of the buffer layer is Negative electrolyte or Positive electrolyte may be the same as, or Negative electrolyte and the concentration of Positive electrolyte The buffer layer may have a concentration between Negative electrolyte and Positive electrolyte Of course, there is a restriction on the movement of ions between Negative electrolyte and Positive electrolyte To help prevent mixing between Negative electrolyte or Positive electrolyte The viscosity may be higher than either of the above.

[0061]

[0065] As shown in Figures 1A to 1D, Positive electrolyte 3 may be in contact with the cathode 12, Negative electrolyte 6 may be in contact with the anode 13. As described in more detail herein, Positive electrolyte 3 and / or Negative electrolyte One or both of 6 may be polymerized or gelled to form a separate gel electrolyte to prevent mixing between the two electrolyte solutions. Positive electrolyte 3 may be disposed within the housing 10 in contact with the cathode material 2. In some embodiments, Negative electrolyte 6 can be polymerized or gelled; Positive electrolyte 3 can be a liquid. Positive electrolyte 3 can be polymerized or gelled; Negative electrolyte 6 can be a liquid. Negative electrolyte Polymerization of 6 is Positive electrolyte Even when 3 is liquid, Positive electrolyte 3 and Negative electrolyte 6. Positive electrolyte The polymerization of 3 is Negative electrolyte Even when 6 is liquid, Positive electrolyte 3 and Negative electrolyte 6. In some embodiments, Positive electrolyte 3 and Negative electrolyte Both of the six gels.

[0062]

[0066] As disclosed herein, the cathode and anode side electrolytes may be separated. Positive electrolyte 3) is usually preferably an acid, and the anodic electrolyte (e.g., Negative electrolyte 6), a base is usually preferred. However, the electrolyte can be easily exchanged between the two electrodes as needed. The electrolytes disclosed herein (e.g., Positive electrolyte 3. Negative electrolyte Non-limiting examples of acids suitable for use in 6) include hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, hydroiodic acid, triflic acid, or any combination thereof. Triflic acid is a superacid with high proton activity, and the use of these acids can contribute to significant performance improvements. The electrolytes disclosed herein (e.g., Positive electrolyte 3. Negative electrolyteNon-limiting examples of bases suitable for use in 6) include ammonia, methylamine, glycine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, or any combination thereof.

[0063]

[0067] Acidic electrolytes (e.g., Positive electrolyte 3. Negative electrolyte 6) has a relatively high proton activity, which determines the battery potential. The higher the proton activity in the electrolyte, the higher the battery potential. The acid dissociation constant (K a ) is a relatively good indicator for determining the activity of protons. Positive electrolyte 3. Negative electrolyte 6) of acidic electrolytes or ions suitable for use in a Non-limiting examples of acids ranging from low to very high include hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, hydroiodic acid, triflic acid, or any combination thereof. Positive electrolyte 3 contains an acidic electrolyte.

[0064]

[0068] Electrolytes (e.g., Positive electrolyte 3. Negative electrolyte 6) can be an acidic solution whose pH can be less than about 4, alternatively less than about 3, alternatively less than about 2, alternatively less than about 1, alternatively between -1.2 and 4, alternatively between -1.2 and 3, alternatively between -1.2 and 2, alternatively between -1.2 and 1. An electrolyte (e.g., Positive electrolyte 3. Negative electrolyte 6) can be used in temperature conditions ranging between 0° C. and 200° C. In some embodiments, the electrolyte (e.g., Positive electrolyte 3. Negative electrolyte6) can include an acid such as a mineral acid (e.g., hydrochloric acid, nitric acid, sulfuric acid, etc.). In the case of an acidic electrolyte composition, the acid concentration (e.g., the concentration of the acidic electrolyte) can be between about 0.0001 M and about 16 M, alternatively about 0.001 M to about 16 M, alternatively about 0.01 M to about 16 M, alternatively about 0.1 M to about 16 M, alternatively about 1 M to about 16 M.

[0065]

[0069] In some embodiments, an acidic electrolyte (e.g., Positive electrolyte 3. Negative electrolyte The hydrogen activity of 6) can be modified by using acids of different strengths. a is a relatively good indicator of acid strength. a The following electrolytes or ions, ranging from low to very high, can be used: hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, hydroiodic acid, triflic acid, or any combination thereof. While these examples of acidic electrolytes can be useful for modifying hydrogen (or proton) activity, it will be apparent to those skilled in the art of chemistry or electrochemistry that any combination of acidic electrolytes with other electrolytes can be used to modify proton activity.

[0066]

[0070] Alkaline electrolytes (e.g., Positive electrolyte 3. Negative electrolyte 6) has a relatively high hydroxyl activity, which determines the battery potential. The higher the hydroxyl activity in the electrolyte, the higher the battery potential. Positive electrolyte 3. Negative electrolyte Non-limiting examples of alkaline electrolytes or ions with relatively high hydroxyl activity suitable for use in 6) include ammonia, methylamine, glycine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, or any combination thereof. Negative electrolyte 6 includes a basic electrolyte (eg, an alkaline electrolyte).

[0067]

[0071] In some embodiments, Negative electrolyte may be an alkaline electrolyte (e.g., a relatively alkaline electrolyte), Positive electrolyte may be an acidic solution (eg, a relatively highly acidic solution).

[0068]

[0072] The alkaline electrolyte can be a hydroxide, such as potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, cesium hydroxide, or any combination thereof. Positive electrolyte 3. Negative electrolyte 6) can have a pH of 10 or greater, alternatively 11 or greater, alternatively 12 or greater, or alternatively 13 or greater. In some embodiments, the alkaline electrolyte (e.g., Positive electrolyte 3. Negative electrolyte 6) may have a pH of about 10 or more and about 15.13 or less, alternatively about 11 or more and about 15.13 or less, alternatively about 12 or more and about 15.13 or less, alternatively about 13 or more and about 15.13 or less. As described herein, electrolytes (e.g., Positive electrolyte 3. Negative electrolyte 6) can be polymerized or gelled. The resulting electrolyte can be in a semi-solid state that resists flow within the battery. This is Negative electrolyte and Positive electrolyte This can help limit or prevent mixing of electrolytes (e.g., Positive electrolyte 3. Negative electrolyte 6) may be polymerized using any suitable technique, including any of the techniques described herein. In some embodiments, the alkaline electrolyte is Negative electrolyte 6 and / or Positive electrolyte 3, in an amount of 1 to 70 wt%, alternatively 1 to 25 wt%, alternatively 25 to 70 wt%, alternatively 20 to 60 wt%, alternatively 20 to 55 wt%, alternatively 30 to 55 wt%, alternatively 1 to 60 wt%, alternatively 1 to 55 wt%, alternatively 5 to 60 wt%, alternatively 10 to 60 wt%, alternatively 20 to 60 wt%, based on the total weight of Negative electrolyte 6 and / or Positive electrolyte3. Typically, a higher concentration of alkaline electrolyte is used to increase the solubility of the metal ions in the gelled state in the electrolyte. For example, a higher concentration of alkaline electrolyte can Negative electrolyte 6 and / or Positive electrolyte 3. The amount of 3 may be between 25 and 70% by weight.

[0069]

[0073] In some embodiments, an electrolyte (e.g., Positive electrolyte 3. Negative electrolyte The hydroxyl activity of 6) can be modified by using bases of different strengths, from low to high, including ammonia, methylamine, glycine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, or any combination thereof. While these examples of alkaline electrolytes can be useful for modifying the hydroxyl activity, it will be apparent to those skilled in the art of chemistry or electrochemistry that any combination of alkaline electrolytes with other electrolytes can be used to modify the hydroxyl activity.

[0070]

[0074] The electrolyte additives can help improve the performance of the cathode and anode materials. The acidic electrolytes disclosed herein (e.g., acidic cathode electrolytes, Positive electrolyteNon-limiting examples of electrolyte additives suitable for use in 3) include manganese sulfate, nickel sulfate, potassium permanganate, manganese chloride, manganese acetate, manganese triflate, bismuth chloride, bismuth nitrate, manganese nitrate, nickel sulfate, nickel nitrate, zinc sulfate, zinc chloride, zinc acetate, zinc triflate, indium chloride, copper sulfate, copper chloride, lead sulfate, sodium persulfate, potassium persulfate, ammonium persulfate, ammonium chloride, vanillin, potassium chloride, sodium chloride, lithium nitrate, lithium chloride, lithium carbonate, lithium acetate, lithium triflate, aluminum trifluoromethanesulfonate, aluminum chloride, aluminum nitrate, potassium sulfate, sodium sulfate, ammonium sulfate, potassium bicarbonate, sodium bicarbonate, or any combination thereof. The concentration of the electrolyte additive in the electrolyte can be between 0M and 5M. The basic electrolytes disclosed herein (e.g., alkaline anode electrolytes, Negative electrolyte Non-limiting examples of electrolyte additives suitable for use in 6) include vanillin, indium hydroxide, zinc acetate, zinc oxide, manganese acetate, cetyltrimethylammonium bromide, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, polyethylene glycol, ethanol, methanol, zinc gluconate, manganese gluconate, manganese acetate, glucose, or any combination thereof.

[0071]

[0075] Acidic electrolytes (e.g., Positive electrolyte 3) Additives can help improve the performance of electrode materials (e.g., cathode materials). Acidic electrolyte additives suitable for use in the present disclosure (e.g., Positive electrolyteNon-limiting examples of the additive (additive) include manganese sulfate, nickel sulfate, potassium permanganate, manganese chloride, manganese acetate, manganese triflate, bismuth chloride, bismuth nitrate, manganese nitrate, nickel sulfate, nickel nitrate, zinc sulfate, zinc chloride, zinc acetate, zinc triflate, indium chloride, copper sulfate, copper chloride, lead sulfate, sodium persulfate, potassium persulfate, ammonium persulfate, ammonium chloride, vanillin, potassium chloride, sodium chloride, lithium nitrate, lithium chloride, lithium carbonate, lithium acetate, lithium triflate, aluminum trifluoromethanesulfonate, aluminum chloride, aluminum nitrate, potassium sulfate, sodium sulfate, ammonium sulfate, or any combination thereof. Positive electrolyte The concentration of the additive can be between 0M and 5M.

[0072]

[0076] In some embodiments, the acidic electrolyte solution (e.g., catholyte solution) may be potassium permanganate, sodium permanganate, lithium permanganate, calcium permanganate, manganese sulfate, manganese chloride, manganese nitrate, manganese perchlorate, manganese acetate, manganese bis(trifluoromethanesulfonate), 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 The catholyte solution may include a solution containing sodium, 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 catholyte solution may include manganese sulfate mixed with sulfuric acid or potassium permanganate mixed with sulfuric acid. Other dopants for this solution may be zinc sulfate, lead sulfate, titanium disulfide, titanium sulfate hydrate, silver sulfate, cobalt sulfate, and nickel sulfate. In some embodiments, the catholyte solution can include manganese sulfate, ammonium chloride, ammonium sulfate, manganese acetate, potassium permanganate, and / or permanganate salts, with the additive concentration being between 0M and 10M. Depending on the type of manganese salt used, the voltage of the battery system can vary. For example, with a manganese sulfate electrolyte, the voltage of the SS-HiVAB is approximately 2.45-2.5 V, while with a potassium permanganate electrolyte, the voltage of the SS-HiVAB is approximately 2.8-2.9 V.

[0073]

[0077] In some embodiments, an acidic electrolyte (e.g., Positive electrolyte3) can include permanganate. Permanganate has a high positive potential, which can enable an increase in the overall cell potential within battery 10. If present, permanganate can be present in a molar ratio of permanganate to acid (e.g., a mineral acid, such as hydrochloric acid or sulfuric acid) of about 5:1 to 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 can vary based on the expected operating conditions of battery 10. The concentration of permanganate (e.g., potassium permanganate or a permanganate salt) can be greater than 0 and less than or equal to 5M. In some embodiments, the acidic electrolyte solution (e.g., cathode solution) contains sulfuric acid, hydrochloric acid, or nitric acid at a concentration greater than 0.0001M and less than or equal to 16M. The use of permanganate can be advantageous in the construction of high-voltage batteries. Positive electrolyte When includes a permanganate, suitable permanganates may include, but are not limited to, potassium permanganate, sodium permanganate, lithium permanganate, calcium permanganate, and combinations thereof.

[0074]

[0078] In addition to hydroxides, alkaline electrolytes (e.g., Negative electrolyte 6) may contain additional components. In some embodiments, the alkaline electrolyte may have zinc oxide, potassium carbonate, potassium iodide, and potassium fluoride as additives. Negative electrolyte If present in Negative electrolyte may include zinc sulfate, zinc chloride, zinc acetate, zinc carbonate, zinc chlorate, zinc fluoride, zinc formate, zinc nitrate, zinc oxalate, zinc sulfite, zinc tartrate, zinc cyanide, zinc oxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium chloride, sodium chloride, potassium fluoride, lithium nitrate, lithium chloride, lithium bromide, lithium bicarbonate, lithium acetate, lithium sulfate, lithium permanganate, lithium nitrate, lithium nitrite, lithium perchlorate, lithium oxalate, lithium fluoride, lithium carbonate, lithium bromate, acrylic acid, N,N'-methylenebisacrylamide, potassium persulfate, ammonium persulfate, sodium persulfate, or combinations thereof.

[0075]

[0079] In some embodiments, an alkaline electrolyte (e.g., Negative electrolyte 6) may contain an electrolyte additive (e.g., vanillin, indium hydroxide, zinc acetate, zinc oxide, cetyltrimethylammonium bromide, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, polyethylene glycol, ethanol, methanol, zinc gluconate, manganese gluconate, manganese acetate, glucose, or any combination thereof) Negative electrolyte additives).

[0076]

[0080] 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 containing the salt described herein can be: Negative electrolyte and / or Positive electrolyte The catalyst may be used with an organic solvent to form an organic electrolyte for use in a semiconductor device.

[0077]

[0081] In some embodiments, the ionic liquid is a gel electrolyte (e.g., a gelled Negative electrolyte , gelled Positive electrolyteIonic liquids can be used to form electrolytes such as EMImCl, 1-ethyl-3-methylimidazolium chloride (EMImCl), 1-allyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium chloride, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium tetrachloroaluminate, lithium hexafluorophosphate (LiPF), lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(oxalato)borate, and combinations thereof. Other ionic liquids are known and can also be used. In some embodiments, EMImCl can be used as the ionic liquid and purified before being mixed with an aluminum salt to form an aluminum ion-conducting electrolyte. The aluminum salt can be aluminum chloride, aluminum acetate, aluminum nitrate, aluminum bromide, or the like. The mixture of EMImCl and aluminum chloride can be prepared by slowly adding the correct amount of aluminum chloride in an inert atmosphere. The ratio of aluminum chloride to EMImCl can be between 5:1 and 1:1, or about 1.5:1.

[0078]

[0082] In some embodiments, the water-in-salt electrolyte is gelled; Positive electrolyte and / or Negative electrolyte Water-in-salt electrolytes can include electrolytes where the salt concentration exceeds the saturation point. The activity of water in aqueous electrolytes can be further reduced by increasing the salt concentration beyond the saturation point to form water-in-salt electrolytes. The ionic conductivity of such electrolytes can be higher than that of typical aqueous electrolytes. Water-in-salt electrolytes can be used in aqueous electrolytes. Negative electrolyte and / or aqueous Positive electrolyte It may contain water with an appropriate salt above its saturation point, including any of the salts and additives described herein.

[0079]

[0083] To prevent neutralization, Negative electrolyte and Positive electrolytemust be kept separate or isolated. Such separation can be achieved by the use of a separator, through gelation or polymerization of the electrolyte, and any combination thereof.

[0080]

[0084] Negative electrolyte and Positive electrolyte One or both of the electrolytes may be gelled within the battery. The polymerization process may be carried out with any electrolyte, including any of those described herein (e.g., organic, aqueous, ionic liquid, water-in-salt, etc.). Several polymerization techniques may be used to form the gel / solid electrolyte, such as, for example, step-growth, chain-growth, emulsion polymerization, solution polymerization, suspension polymerization, precipitation polymerization, photopolymerization, etc. Once the gel / solid electrolytes are formed through the polymerization step, they may be combined into a single battery housing as described herein. The battery may use a separator or may be membraneless or separatorless.

[0081]

[0085] As described herein, the electrolyte may be polymerized or gelled to form a Positive electrolyte and / or Negative electrolyteA polymer gel electrolyte (PGE) for use in a battery can be formed. The resulting PGE can be in a semi-solid state that resists flow within the battery. For example, the PGE can include an inert hydrophilic polymer matrix impregnated with an aqueous electrolyte. The electrolyte can be polymerized using any suitable technique. In one embodiment, a method for forming a PGE can begin with the selection of a monomer material for the PGE. The monomer can be a polar vinyl monomer selected from the group consisting of acrylic acid, vinyl acetate, acrylic ester, vinyl isocyanate, acrylonitrile, or any combination thereof. The components of the aqueous electrolyte can then be selected and can include any of the above components for the electrolyte. To begin the polymerization process, an initiator can be added. In some embodiments, a crosslinker can be used in the electrolyte composition to further crosslink the polymer matrix to form the PGE. The monomer (e.g., polar vinyl monomer) in the composition can be present in an amount between about 5% and about 50% by weight, the initiator can be present in an amount between about 0.001% and about 0.1% by weight, and the crosslinker can be present in an amount between 0 and 5% by weight.

[0082]

[0086] In some embodiments, the PGE may be formed in situ, which refers to introducing the electrolyte into the housing as a liquid and subsequently polymerizing to form the PGE within the housing. This method may allow the electrolyte composition to soak into the voids, anode, and / or cathode before fully polymerizing to form the PGE. In some embodiments, a vacuum (e.g., a pressure less than atmospheric pressure) may be created within the housing 7 upon introduction of the electrolyte into the corresponding compartments. The vacuum may help remove air and allow the electrolyte to penetrate the anode 13, the cathode 12, and / or various voids within the battery 10. In some embodiments, the vacuum may be between about 10 and 29.9 inches of mercury, or between about 20 and 29.9 inches of mercury. The use of a vacuum may help avoid the presence of air pockets within the battery 10 prior to full polymerization of the electrolyte. In some embodiments, the electrodes may be immersed in the electrolyte solution for 1 to 120 minutes at a temperature between 0°C and 30°C prior to full polymerization of the electrolyte to allow the electrolyte to impregnate the electrodes. Once the electrolyte is polymerized, the battery may be allowed to rest before use. In some embodiments, the battery may be allowed to rest for between 5 minutes and 24 hours.

[0083]

[0087] To aid in impregnating the electrodes with the electrolyte, the electrodes may be pre-soaked in the selected electrolyte solution prior to polymerizing the electrolyte. This is advantageous over pre-soaking the electrolyte on the outside of the battery or housing (e.g., Positive electrolyte or Negative electrolyteThis can be done by soaking the electrodes (separately) and then placing the pre-soaked electrodes in a housing to construct the battery. In some embodiments, an electrolyte without a polymer or gelling agent can be introduced into the battery to soak the electrodes in situ. This can include the use of a vacuum to assist in the impregnation of the electrodes. The electrodes can be soaked for between about 1 minute and 24 hours. In some embodiments, soaking can be done over multiple cycles, where the battery is filled with electrolyte, allowed to soak, drained, refilled, and allowed to soak and drain as many times as desired. Once the electrodes are soaked and impregnated with the electrolyte, the electrolyte, including the polymer and polymerization agent (e.g., initiator, crosslinker, etc.), can be introduced into the housing and allowed to polymerize to form the final battery.

[0084]

[0088] The electrolyte composition, monomer material, initiator, and formation conditions (e.g., temperature, etc.) can be selected to provide a desired polymerization time that allows the electrolyte composition to adequately soak the battery components and absorb and penetrate the electrodes. The temperature can be controlled to control the polymerization process; a relatively low temperature can inhibit or slow polymerization, while a relatively high temperature can shorten the polymerization time or accelerate the polymerization process. Additionally, increasing the alkaline electrolyte component (e.g., hydroxide) can shorten the polymerization time, and increasing the initiator concentration will shorten the polymerization time. Suitable polymerization times can be between 1 minute and 24 hours, depending on the composition of the electrolyte solution and the temperature of the reaction.

[0085]

[0089] In some embodiments, Negative electrolyte and / or Positive electrolyte can be formed via a gelation process such as a free radical polymerization technique, in which, for example, acrylic acid can be used as a monomer. The acrylic acid can be dissolved until substantially dissolved. Negative electrolyte or Positive electrolyte Crosslinkers such as N,N'-methylenebisacrylamide (MBA) can be used to increase the strength of the polymer. Acidic electrolytes (e.g., Negative electrolyteIn the case of alkaline electrolytes (e.g., Positive electrolyte ), a mixture of acrylic acid and MBA can be heated to 50-200°C. Polymerization can be initiated through the addition of an initiator such as a persulfate salt, such as potassium persulfate, sodium persulfate, ammonium persulfate, or any combination thereof. The electrolyte additives disclosed herein (e.g., Negative electrolyte additives, Positive electrolyte Additives) may be included during the gelation process. Ionomers may also be added during the gelation process. Non-limiting examples of ionomers that may be added to the electrolyte during the gelation process include perfluorosulfonic acid (PFSA) / polytetrafluoroethylene (PTFE) copolymer in its acid form, or Nafion solutions made from anion exchange ionomers with polyaromatic polymers.

[0086]

[0090] As an example of a polymerization process, a mixture of acrylic acid, N,N'-methylenebisacrylamide, and an alkaline solution can be generated at a temperature of about 0°C. Any additives can then be added to the solution (e.g., gassing inhibitors, additional additives described herein, etc.). For example, if an electrolyte additive is used in the electrolyte, it can be dissolved in the alkaline solution after mixing the precursor components, and the electrolyte additive can be beneficial during the electrochemical cycling of the electrode. To polymerize the resulting mixture, an initiator such as potassium persulfate can be added to start the polymerization process and form a solid or semi-solid polymerized electrolyte (e.g., PGE). The resulting polymerized electrolyte can be stable over time once the polymerization process occurs.

[0087]

[0091] As an example, the PGEs described herein can be made through a free radical polymerization process. In one embodiment, acrylic acid (AA) can be used as a monomer, along with N,N'-methylenebisacrylamide (MBA) as a crosslinker and potassium persulfate (KSO) as an initiator. Negative electrolyteWhen preparing the solution, an alkaline electrolyte such as KOH may be added to the process. Negative electrolyte It can be embedded in a gel / polymer framework. The addition of alkaline electrolyte to AA results in neutralization, reducing the concentration of alkaline electrolyte in the polymer gel. Different concentrations of alkaline electrolyte can change the gelation time. Higher concentrations of alkaline electrolyte usually result in faster gelation, while lower concentrations of alkaline electrolyte take longer. The initiator concentration can also affect the gelation process. Furthermore, the viscosity of the gel can be adjusted by changing the concentrations of the monomer and MBA, which can also affect the ionic conductivity. Similarly, Positive electrolyte When preparing the acid electrolyte, such as sulfuric acid, may be added to the process. Positive electrolyte It may be embedded in a gel / polymer framework.

[0088]

[0092] In some embodiments, an ionomer gelling layer may also be created, which may separate the catholyte and anolyte solutions, or their gels. The gelling process for forming the ionomer gelling layer may be any of the methods described herein. Negative electrolyte Gel and / or Positive electrolyte The gelation process is substantially similar to the gelation process that forms the gel, in which an ionomer is added to the electrolyte during the gelation process. The ionomer gel (e.g., the ionomer gelling layer) may also include additives such as potassium sulfate, sodium sulfate, ammonium sulfate, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, or any combination thereof. An ionomer resin may also be used in the gelation process to produce the ionomer gelling layer.

[0089]

[0093] The polymerization process can occur before construction of the battery 10 or after the cells are constructed. In some embodiments, the electrolyte can be polymerized and placed in trays to form sheets. Once polymerized, the sheets can be cut to the appropriate size and shape, and one or more layers can be used to form the electrolyte in contact with the electrodes. If a preformed PGE is used, additional liquid electrolyte can be introduced into the battery and / or the electrodes can be pre-soaked in the electrolyte before constructing the battery.

[0090]

[0094] In some embodiments, the PGE may be formed using aqueous electrolytes, organic electrolytes, ionic liquids, water-in-salt electrolytes, etc. In some embodiments, the aqueous electrolyte is Positive electrolyte and / or Negative electrolyte and can be gelled to form aqueous hydrogels as PGEs. In some embodiments, aqueous hydrogels can be made through a free radical polymerization process. For example, Negative electrolyte When preparing the above, acrylic acid (AA) can be selected as the monomer, together with N,N'-methylenebisacrylamide (MBA) as the crosslinker and potassium persulfate as the initiator. Negative electrolyte In the method, a suitable hydroxide (e.g., potassium hydroxide (KOH), sodium hydroxide, lithium hydroxide, etc.) can be used to form the electrolyte. By neutralizing the hydroxide with AA, the hydroxide can be entrapped in the hydrogel network. To create the hydrogel, the monomer can be combined with an optional crosslinker until the crosslinker is dissolved. Alternatively, a quantity of hydroxide can be cooled to slow the reaction. Negative electrolyteIn some embodiments where the hydroxide is an aqueous electrolyte, the hydroxide can be cooled to a temperature below about 10°C, below about 5°C, or below about 0°C. The mixed solution of the monomer and optional crosslinker can then be added dropwise to the cooled hydroxide solution as the neutralization reaction releases heat. An initiator, such as potassium persulfate, can be added to gel the resulting mixture of hydroxide, monomer, and crosslinker. The mixture can then be allowed to form a PGE. The amounts and concentrations of the components can be varied to obtain different mechanical strengths of the hydrogel. Similarly, Positive electrolyte When preparing the hydrogel, an acidic electrolyte such as sulfuric acid can be entrapped in the hydrogel network.

[0091]

[0095] Electrolytes containing ionic liquids can also be used to form PGEs containing any of the ionic liquids described herein. To form PGEs using ionic liquids, a solution of any additives, which may be contained in a suitable solvent, can be prepared, and a monomer can be added. The monomer can be any suitable monomer. For example, acrylamide can be used as a polymerization agent for the ionic liquid. To this solution, the ionic liquid along with the additive solution can be mixed with an initiator. Any suitable initiator for use with the polymerization agent can be used. For example, azobisisobutyronitrile can be used with acrylamide. The initiator can be added in an appropriate amount, such as about 1% by weight of the polymerization agent. This final solution can then be heated to form a polymerized gel.

[0092]

[0096] Organic electrolytes, which include salts dissolved in organic solvents, also include: Negative electrolyte and / or Positive electrolyteAs an example, lithium ion conducting electrolytes can be gelled to form a lithium ion conducting electrolyte. As an example, lithium ion conducting electrolytes can be gelled using several polymerization techniques, such as ring-opening polymerization, photoinitiated radical polymerization, UV-initiated radical polymerization, thermally initiated polymerization, in situ polymerization, UV irradiation, and electrospinning. The lithium electrolyte can include lithium hexafluorophosphate (LiPF), lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(oxalato)borate, and combinations thereof, in organic solvents such as ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate, and combinations thereof. An exemplary mixture can include 1 M LiPF in a solvent mixture of ethylene carbonate and dimethyl carbonate. There are also other solvents that can be used as mixtures to reduce the flammability of organic electrolytes.

[0093]

[0097] The organic electrolyte can be gelled by mixing a selected salt with an organic solvent. A gelling agent can then be added along with an initiator. The gelling agent can be added in an amount between about 0.1 and about 5% by weight of the mixture, and the initiator can be added in an amount between about 0.01 and about 1% by weight of the mixture. In some embodiments, a suitable gelling agent for the organic electrolyte can include pentaerythritol tetraacrylate, and the initiator can include azodiisobutyronitrile. The resulting mixture can be gelled (e.g., polymerized) by heating the mixture to about 50 to 90°C, or about 70°C, and holding for 1 to 24 hours.

[0094]

[0098] Positive electrolyteFor aqueous electrolytes that are inherently acidic, such as HCl, polymerization can be carried out using a number of processes. In certain embodiments, a method for creating an acidic, solid-state gelling aqueous electrolyte can include adding acrylamide to a solution containing manganese sulfate, H2SO4, ammonium sulfate, potassium permanganate, and / or sulfuric acid. The gelling agent, including acrylamide, can be added to the solution and mixed at a temperature between about 70 and 90°C for at least one hour until the solution is homogeneous. After the solution is thoroughly mixed, a crosslinker and initiator can be added to the solution and mixed for 2 to 48 hours until the solution gels.

[0095]

[0099] In some embodiments, the separator comprises an ion-selective gel, which comprises an ionomer, a bipolar membrane, a cation exchange membrane, an anion exchange membrane, ion-selective grafted cellophane, ion-selective grafted polyvinyl alcohol, a ceramic separator, NaSiCON, LiSiCON, or any combination thereof.

[0096]

[0100] Negative electrolyte PGE and Positive electrolyte PGE can be used without a separator, Positive electrolyte and Negative electrolyte Separation of ions can also be achieved through ion-selective ceramic separators and / or polymeric membranes. Cellulose-based membranes such as cellophane can also be used. Positive electrolyte and Negative electrolyte For example, ceramic separators such as LiSiCON and / or NaSiCON can be used to separate Positive electrolyte and Negative electrolyte As another example, polymer membranes with cation exchange properties, such as Nafion, and / or anion exchange membranes can be used to separate: Positive electrolyte and Negative electrolyte Polyvinyl alcohol (PVA) and / or cross-linked polyvinyl alcohol (C-PVA) can also be used to separate Positive electrolyte and Negative electrolyteCellulose-based membranes, PVA, and C-PVA can be grafted with ionomers that can impart cation and / or anion exchange properties. Bipolar membranes can also be used as polymer separators to separate Positive electrolyte and Negative electrolyte It can be used as a separator between

[0097]

[0101] Gel or polymer membranes containing LiSiCON and NaSiCON can be made using the procedures described herein for the formation of PGE and / or ionomer gelled layers by using the raw materials used to make ceramic separators.

[0098]

[0102] The cathodes and anodes used in the high voltage metal-free batteries disclosed herein can advantageously approach 5-100%, or alternatively 50-100%, of theoretical capacity over a wide range of current densities and material loadings.

[0099]

[0103] The high voltage metal-free battery disclosed herein does not have the problem of display dendrites or short circuits due to the absence of metal electrodes.

[0100]

[0104] The final cell or battery design may include an acidic PGE with a separator or buffer layer to prevent mixing of the two PGEs. Positive electrolyte and a cathode containing alkaline PGE Negative electrolyte Anodes containing: Batteries with dual electrolytes allow for high reversibility and improved or maximized utilization of the electrodes, and thus higher energy density. Negative electrolyte and Positive electrolyte The use of widely differing alkalinities and acidities in the battery further allows the average discharge of the battery to be increased to above about 1.6V.

[0101]

[0105] In some embodiments, the high-voltage metal-free battery disclosed herein can be used to generate energy. For example, a method of generating energy can include (i) discharging the high-voltage metal-free battery disclosed herein to a discharge voltage to generate energy, wherein at least a portion of the anode electroactive material is oxidized to form an oxidized anode material during discharge, and (ii) charging the high-voltage metal-free battery to a charge voltage, wherein at least a portion of the oxidized anode material is reduced to the oxidized anode material during charge. The discharge voltage can be greater than 1.6 V, alternatively about 2 V or greater, alternatively about 3 V or greater, alternatively about 3.5 V or greater, alternatively about 1.6 V to about 5 V, alternatively about 2 V to about 5 V, alternatively about 3 V to about 5 V, or alternatively about 3.5 V to about 5 V.

[0102] Example

[0106] Having generally described the subject matter, the following examples are provided as particular embodiments of the disclosure and are included to demonstrate its practice and advantages, as well as preferred aspects and features of the invention. Those of skill in the art should appreciate that the techniques disclosed in the examples that follow represent techniques discovered by the inventors to function well in the practice of the invention, and therefore can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments disclosed and still obtain like or similar results without departing from the inventive scope of this disclosure. It should be understood that the examples are given by way of illustration and are not intended to limit the scope of the claims which follow in any way.

[0103] Example 1

[0107] A schematic diagram of a battery with a prismatic geometry is shown in Figure 1A. The battery can be of any geometric form factor and can be flexible. It can be scaled up to any size (physical and capacity (Ah)) depending on the application to be served. Figure 1A shows a schematic diagram of a high-voltage metal-free battery.

[0104]

[0108] Manganese dioxide (MnO2), more specifically electrolytic manganese dioxide (EMD), was chosen as an exemplary cathode system. The OCV of a conventional or traditional alkaline MnO2|Zn battery is approximately 1.6 V. In a high-voltage metal-free MnO2|hausmannite (Mn3O4) aqueous battery, the OCV is used Positive electrolyte and Negative electrolyte In the case of rechargeable batteries, the concentration of Positive electrolyte was 3M sulfuric acid containing 0.5M manganese sulfate as an additive, and was used Negative electrolyte The electrolyte was 25 wt% potassium hydroxide. The cathode composition was 80 wt% MnO2, 15 wt% expanded graphite, and 5 wt% Teflon coated on a titanium current collector. The anode composition was similar, with bismuth oxide as an additive coated on a nickel current collector. Nafion 115 was used as the ion-selective membrane separator. The OCV of this battery was approximately 1.6 V. The cathode and anode were monitored relative to a reference electrode, and the potentials are shown in Figure 2, along with the battery voltage. Figure 2 shows the performance of a rechargeable electrolytic manganese dioxide (MnO2)|hausmannite (Mn3O4) battery in terms of battery voltage versus Mn3O4, cathode (MnO2) versus mercury|mercury oxide (Hg|HgO), and anode (Mn3O4) versus a Hg|HgO reference electrode. Positive electrolyte were 3M sulfuric acid and 0.5M manganese sulfate. Negative electrolyte The MnO2 was 25 wt% potassium hydroxide. The MnO2 was cycleable to 1-electron (308 mAh / g) and 2-electron (617 mAh / g) capacities. The battery could be cycled many times at rated capacity without loss of voltage or capacity, as shown in Figure 2.

[0105] Example 2

[0109] Another high-voltage metal-free MnO2|Mn3O4 aqueous battery was assembled with the same cathode and anode mix composition as described in Example 1, unless otherwise indicated herein. MnO2|Mn3O4 with similar experimental details as described in Example 1 was assembled for first discharge testing and compared to a conventional or legacy alkaline MnO2|Zn battery. Positive electrolyte is 16M sulfuric acid, while Negative electrolyte The electrolyte used in the new metal-free battery was 45 wt. % potassium hydroxide. The OCV of this battery was approximately 2.2 V, 0.6 V higher than that of a conventional alkaline battery. In terms of discharge performance, the new metal-free battery was able to deliver higher energy compared to that delivered by a conventional alkaline battery, as shown in Figure 3. Figure 3 shows a comparison of the discharge curves of the new metal-free electrolytic manganese dioxide (MnO2)|hausmannite (Mn3O4) battery and a conventional electrolytic manganese dioxide (MnO2)|zinc (Zn) battery. The electrolyte used in the new metal-free MnO2|Mn3O4 battery was Positive electrolyte as 16M sulfuric acid, Negative electrolyte The electrolyte used in the conventional MnO2|Zn battery was 45 wt% potassium hydroxide (KOH). As shown in Figure 3, the new MnO2|Mn3O4 battery can outperform the conventional MnO2|Zn battery in terms of energy and capacity. The electrolyte used in the conventional MnO2|Zn battery was 25 wt% potassium hydroxide (KOH).

[0106] Example 3

[0110] The characteristics of another high-voltage metal-free MnO2|Mn3O4 aqueous battery were investigated. The cathode was similar to the cathode described in Examples 1 and 2. The anode of Example 3 was manganese oxide (MnO) with a theoretical capacity of approximately 750 mAh / g. This anode (MnO) had a composition similar to that described for the anode of Example 1, but contained bismuth oxide as an electrode additive. This anode material (MnO-based anode) was attached to a nickel mesh with copper as a backing. The discharge performance of this new battery chemistry, MnO2|MnO, was tested by measuring the voltages of each cathode and anode separately, and the data are displayed in Figure 4. Figure 4 shows the discharge capacity of an electrolytic manganese dioxide (MnO2)|manganese oxide (MnO) battery used. Positive electrolyte The additives used were 5M sulfuric acid and 3.2M manganese sulfate. Negative electrolyte The electrolyte was 25% by weight potassium hydroxide. The average discharge voltage of this battery was approximately 1.7 V, higher than that of a conventional or legacy alkaline battery. The MnO2 cathode was tested and was able to achieve a theoretical second electron capacity. In more concentrated acidic electrolytes, the cathode appears to undergo a direct dissolution-precipitation reaction, as evidenced by the flatness of the cathode curve. MnO is known to undergo a direct dissolution-precipitation reaction.

[0107] Example 4

[0111] The properties of another high-voltage metal-free battery were investigated. The cathode used was γ-MnO2. This cathode was prepared in situ by the conversion of electrolytic manganese dioxide. The cathode formulation was similar to that of the cathode described in Example 1. The anode in Example 4 was birnessite (δ-MnO2). This new system (γ-MnO2 | δ-MnO2) marks the first demonstration in the patent or academic literature of a complete, single-redox-active Mn-element battery in which both the cathode and anode are MnO2. δ-MnO2 can be synthesized ex situ or in situ. δ-MnO2 was prepared in situ through a formation process starting with electrolytic manganese dioxide mixed with bismuth oxide and copper. After formation, the cathode is copper-intercalated bismuth birnessite. The anode used in Example 4 had a composition similar to that described in Example 1 and was applied to a nickel mesh. The discharge performance of this new battery chemistry, γ-MnO2|δ-MnO2, was tested by measuring the voltages of the cathode and anode separately, as shown in Figure 5. Figure 5 displays the discharge capacity of a gamma-manganese dioxide (γ-MnO2)|birnessite (δ-MnO2) battery used. Positive electrolyte was 3.5M sulfuric acid containing 3.2M manganese sulfate, and Negative electrolyte The electrolyte was 25 wt. % potassium hydroxide. The average discharge voltage of this battery was approximately 1.7 V, higher than that of conventional or legacy alkaline batteries. A sigmoidal curve indicating proton insertion and a flat curve indicating the dissolution-precipitation of γ-MnO2 are seen in Figure 5. The cathode is theoretically capable of up to 617 mAh / g, but the capacity was limited due to different mechanisms. Both the cathode and anode should theoretically deliver 617 mAh / g. This is the first demonstration of this novel γ-MnO2|δ-MnO2 battery chemistry in patent or academic literature.

[0108] Additional Disclosures

[0112] The following is provided as additional disclosure regarding combinations of features and aspects of the subject matter of the present disclosure.

[0109]

[0113] A first aspect is a high voltage metal-free battery comprising a cathode comprising a cathode electroactive material in the form of an organic compound, an oxide, a hydroxide, and a sulfide; an anode comprising an anode electroactive material in the form of an organic compound, an oxide, a hydroxide, and a sulfide; Positive electrolyte a proton-active catholyte solution that is not in contact with the anode but is in contact with the cathode; Negative electrolyte the cathode is not in contact with the anode, the anolyte solution is not in contact with the cathode, and the hydroxyl-active anolyte solution is in contact with the anode, and a separator having ion-selective properties.

[0110]

[0114] A second embodiment is the battery of the first embodiment, wherein the cathode electroactive material is selected from the group consisting of manganese dioxide (MnO2), manganese oxide (Mn2O3, Mn3O4, MnO), manganese hydroxide (MnOOH, Mn(OH)2), silver oxide (AgO, Ag2O), nickel oxide (NiO, Ni2O3), nickel hydroxide (NiOOH, Ni(OH)2), cobalt oxide (Co3O4, CoO), cobalt hydroxide, lead oxide (PbO, PbO2), copper oxide (CuO, Cu2O), hydroxide Copper, potassium iron oxide (K2FeO4), barium iron oxide (BaFeO4), copper hexacyanoferrate, lithium iron phosphate, lithium nickel manganese cobalt oxide, lithium manganese oxide (LiMn2O4, Li2MnO3), calix[4]quinone, 1,4-naphthoquinone, 9,10-anthraquinone, copper sulfide, nickel sulfide, manganese sulfide, tungsten oxide, tin oxide, tin sulfide, tungsten disulfide, vanadium oxide, or combinations thereof.

[0111]

[0115] A third embodiment is the battery of the first embodiment, wherein the anode material is selected from the group consisting of manganese dioxide (MnO2), manganese oxide (Mn2O3, Mn3O4, MnO), manganese hydroxide (MnOOH, Mn(OH)2), silver oxide (AgO, Ag2O), nickel oxide (NiO, Ni2O3), nickel hydroxide (NiOOH, Ni(OH)2), cobalt oxide (Co3O4, CoO), cobalt hydroxide, lead oxide (PbO, PbO2), copper oxide (CuO, Cu2O), copper hydroxide, Potassium iron oxide (K2FeO4), barium iron oxide (BaFeO4), copper hexacyanoferrate, lithium iron phosphate, lithium nickel manganese cobalt oxide, lithium manganese oxide (LiMn2O4, Li2MnO3), calix[4]quinone, 1,4-naphthoquinone, 9,10-anthraquinone, copper sulfide, nickel sulfide, manganese sulfide, tungsten oxide, tin oxide, tin sulfide, tungsten disulfide, vanadium oxide, or combinations thereof.

[0112]

[0116] A fourth embodiment is the battery of the first embodiment, wherein the cathode and anode comprise conductive carbon with cathode and anode active materials comprising graphite, carbon fiber, carbon black, acetylene black, single-walled carbon nanotubes, multi-walled carbon nanotubes, nickel- or copper-coated carbon nanotubes, a dispersion of single-walled carbon nanotubes, a dispersion of multi-walled carbon nanotubes, graphene, graphene, graphene oxide, or combinations thereof.

[0113]

[0117] A fifth embodiment is the battery of the first embodiment, wherein the cathode and anode comprise an additive or dopant comprising bismuth oxide, copper oxide, indium hydroxide, indium oxide, aluminum oxide, nickel hydroxide, nickel oxide, silver oxide, cobalt oxide, cobalt hydroxide, lead oxide, lead dioxide, quinone, or a combination thereof.

[0114]

[0118] A sixth embodiment is the battery of the first embodiment, wherein the cathode and the anode comprise a binder comprising methyl cellulose (MC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPH), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl methyl cellulose (HEMC), carboxymethyl hydroxyethyl cellulose, hydroxyethyl cellulose (HEC), polyvinyl alcohol, TEFLON®, or a combination thereof.

[0115]

[0119] A seventh aspect is the battery of any of the first, second, third, fourth, fifth, and sixth aspects, wherein the cathode and anode are pressed onto a current collector comprising carbon, lead, nickel, steel (e.g., stainless steel), 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, cold-rolled steel, half nickel and half copper, carbon foam, carbon felt, polypropylene mesh, or any combination thereof.

[0116]

[0120] An eighth embodiment is the battery of the seventh embodiment, wherein the current collector can be a foil, a mesh, a perforated foil, a foam, a honeycomb mesh, a sponge shape, or any combination thereof.

[0117]

[0121] A ninth aspect is the battery of any of the first, second, third, fourth, fifth, and sixth aspects, wherein the cathode and anode comprise 1 to 99 wt. % electroactive material, 1 to 99 wt. % conductive carbon, 0 to 30 wt. % additive, and 0 to 10 wt. % binder.

[0118]

[0122] A tenth aspect is a battery according to any one of the first aspects, wherein the battery has a high proton activity. Positive electrolyte comprises hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, hydroiodic acid, triflic acid, or a combination thereof.

[0119]

[0123] An eleventh aspect is the battery of any one of the first and tenth aspects, Positive electrolyte Electrolyte additives to include manganese sulfate, nickel sulfate, potassium permanganate, manganese chloride, manganese acetate, manganese triflate, bismuth chloride, bismuth nitrate, manganese nitrate, nickel sulfate, nickel nitrate, zinc sulfate, zinc chloride, zinc acetate, zinc triflate, indium chloride, copper sulfate, copper chloride, lead sulfate, sodium persulfate, potassium persulfate, ammonium persulfate, ammonium chloride, vanillin, potassium chloride, sodium chloride, lithium nitrate, lithium chloride, lithium carbonate, lithium acetate, lithium triflate, aluminum trifluoromethanesulfonate, aluminum chloride, aluminum nitrate, potassium sulfate, sodium sulfate, ammonium sulfate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, or combinations thereof.

[0120]

[0124] A twelfth aspect is a battery of any of the first aspects, wherein the battery has high hydroxyl activity. Negative electrolyte includes ammonia, methylamine, glycine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, or a combination thereof.

[0121]

[0125] A thirteenth aspect is the battery of either the first or twelfth aspect, Negative electrolyte Electrolyte additives to include vanillin, indium hydroxide, zinc acetate, zinc oxide, cetyltrimethylammonium bromide, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, polyethylene glycol, ethanol, methanol, zinc gluconate, manganese gluconate, manganese acetate, glucose, or a combination thereof.

[0122]

[0126] A fourteenth aspect is the battery of any one of the first, tenth, eleventh, twelfth, and thirteenth aspects, Positive electrolyte and Negative electrolyte may be gelled or polymerised.

[0123]

[0127] A fifteenth embodiment is the battery of the first embodiment, in which the separator comprises an ion-selective gel made from an ionomer, a bipolar membrane, a cation exchange membrane, an anion exchange membrane, cellophane grafted with ion-selective properties, polyvinyl alcohol grafted with ion-selective properties, a ceramic separator such as NaSiCON, LiSiCON, or a combination thereof.

[0124]

[0128] A sixteenth aspect is the battery of either of the first and fifteenth aspects, wherein the separator can be a gelling layer comprised of an ion-selective ionomer and a buffering agent such as potassium carbonate, potassium bicarbonate, sodium carbonate, or sodium bicarbonate, and the ionomer can be an anion exchange ionomer having an acid form of perfluorosulfonic acid (PFSA) / polytetrafluoroethylene (PTFE) copolymer or a polyaromatic polymer.

[0125]

[0129] A seventeenth aspect is a high voltage metal-free battery comprising: a cathode comprising a cathode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; an anode comprising an anode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; and a catalyst in contact with the cathode, the catalyst being not in contact with the anode and having a pH of less than 4. Positive electrolyte and not in contact with the cathode, pH greater than 10, in contact with the anode. Negative electrolyte and,

[0126]

[0130] An eighteenth aspect is the battery of the seventeenth aspect, Negative electrolyte and Positive electrolyte and a separator disposed between the first and second electrodes, the separator having ion-selective properties.

[0127]

[0131] A nineteenth aspect is the battery of either the seventeenth or eighteenth aspect, Negative electrolyte comprises a first gel electrolyte solution; Positive electrolytecomprises a second gel electrolyte solution.

[0128]

[0132] A twentieth embodiment is the battery of any of the seventeenth through nineteenth embodiments, wherein the cathode electroactive material is selected from the group consisting of manganese oxide, manganese dioxide (MnO2), Mn2O3, Mn3O4, MnO; manganese hydroxide, MnOOH, Mn(OH)2; silver oxide, AgO, Ag2O; nickel oxide, NiO, Ni2O3; nickel hydroxide, NiOOH, Ni(OH)2; cobalt oxide, Co3O4, CoO; cobalt hydroxide; lead oxide, PbO, PbO2; copper oxide, CuO, Cu2O; copper hydroxide; acid The present invention relates to an inorganic oxide, and the inorganic oxide may comprise at least one of potassium ferric oxide (K2FeO4); barium iron oxide (BaFeO4); copper hexacyanoferrate; lithium iron phosphate; lithium nickel manganese cobalt oxide; lithium manganese oxide, LiMn2O4, Li2MnO3; calix[4]quinone; 1,4-naphthoquinone; 9,10-anthraquinone; copper sulfide; nickel sulfide; manganese sulfide; tungsten oxide; tin oxide; tin sulfide; tungsten disulfide; vanadium oxide; and any mixture thereof.

[0129]

[0133] A twenty-first embodiment is the battery of any of the seventeenth through twentieth embodiments, wherein the anode electroactive material is selected from the group consisting of manganese oxide, manganese dioxide (MnO2), Mn2O3, Mn3O4, MnO; manganese hydroxide, MnOOH, Mn(OH)2; silver oxide, AgO, Ag2O; nickel oxide, NiO, Ni2O3; nickel hydroxide, NiOOH, Ni(OH)2; cobalt oxide, Co3O4, CoO; cobalt hydroxide; lead oxide, PbO, PbO2; copper oxide, CuO, Cu2O; copper hydroxide; acid The present invention relates to an inorganic oxide, and the inorganic oxide may comprise at least one of potassium ferric oxide (K2FeO4); barium iron oxide (BaFeO4); copper hexacyanoferrate; lithium iron phosphate; lithium nickel manganese cobalt oxide; lithium manganese oxide, LiMn2O4, Li2MnO3; calix[4]quinone; 1,4-naphthoquinone; 9,10-anthraquinone; copper sulfide; nickel sulfide; manganese sulfide; tungsten oxide; tin oxide; tin sulfide; tungsten disulfide; vanadium oxide; and any mixture thereof.

[0130]

[0134] A twenty-second aspect is the battery of any of the seventeenth to twenty-first aspects, wherein the cathode, the anode, or both, comprise conductive carbon, and the conductive carbon is mixed with the cathode electroactive material, the anode electroactive material, or both, respectively, and includes graphite, carbon fiber, carbon black, acetylene black, single-walled carbon nanotubes, multi-walled carbon nanotubes, nickel-coated carbon nanotubes, copper-coated carbon nanotubes, dispersions of single-walled carbon nanotubes, dispersions of multi-walled carbon nanotubes, graphene, graphene oxide, and combinations thereof.

[0131]

[0135] A twenty-third aspect is the battery of any of the seventeenth to twenty-second aspects, wherein the cathode, the anode, or both, include an additive and / or dopant, and the additive and / or dopant includes bismuth oxide, copper oxide, indium hydroxide, indium oxide, aluminum oxide, nickel hydroxide, nickel oxide, silver oxide, cobalt oxide, cobalt hydroxide, lead oxide, lead dioxide, quinone, or a combination thereof.

[0132]

[0136] A twenty-fourth embodiment is the battery of any of the seventeenth to twenty-third embodiments, wherein the cathode, the anode, or both, include a binder, and the binder includes methyl cellulose (MC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPH), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl methyl cellulose (HEMC), carboxymethyl hydroxyethyl cellulose, hydroxyethyl cellulose (HEC), polyvinyl alcohol, TEFLON, or a combination thereof.

[0133]

[0137] A twenty-fifth embodiment is the battery of any of the seventeenth through twenty-fourth embodiments, wherein the cathode, the anode, or both, comprise a cathode material pressed onto a current collector, and the current collector comprises carbon, lead, nickel, steel, stainless steel, nickel-coated steel, nickel-plated copper, tin-coated steel, copper-plated nickel, silver-coated copper, copper, magnesium, aluminum, tin, iron, platinum, silver, gold, bismuth, titanium, cold-rolled steel, half nickel and half copper, polypropylene, or any combination thereof.

[0134]

[0138] A twenty-sixth embodiment is the battery of the twenty-fifth embodiment, wherein the current collector is a foil, a mesh, a perforated foil, a foam, a felt, a fiber, a porous block structure, a honeycomb mesh, a sponge shape, or any combination thereof.

[0135]

[0139] A 27th aspect is the battery of any of the 17th to 26th aspects, wherein the cathode comprises, based on the total weight of the cathode, 1 to 99 wt % of the cathode electroactive material, 1 to 99 wt % of the conductive carbon, 0 to 30 wt % of the additive and / or dopant, and 0 to 10 wt % of the binder.

[0136]

[0140] A 28th aspect is the battery of any of the 17th to 27th aspects, wherein the anode comprises, based on the total weight of the anode, 1 to 99 wt % of the anode electroactive material, 1 to 99 wt % of the conductive carbon, 0 to 30 wt % of the additive and / or dopant, and 0 to 10 wt % of the binder.

[0137]

[0141] A 29th aspect is the battery of any one of the 17th to 28th aspects, Positive electrolyte comprises an acidic electrolyte, the acidic electrolyte comprising at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, hydroiodic acid, triflic acid, and any mixture thereof.

[0138]

[0142] A 30th aspect is the battery of any of the 17th to 29th aspects, wherein the acidic electrolyte has a concentration between about 0.1M and about 16M. Positive electrolyte exists within.

[0139]

[0143] A thirty-first aspect is the battery of any one of the seventeenth to thirtieth aspects, Positive electrolyte teeth Positive electrolyte Contains additives, Positive electrolyte The additive comprises at least one of manganese sulfate, nickel sulfate, potassium permanganate, manganese chloride, manganese acetate, manganese triflate, bismuth chloride, bismuth nitrate, manganese nitrate, nickel sulfate, nickel nitrate, zinc sulfate, zinc chloride, zinc acetate, zinc triflate, indium chloride, copper sulfate, copper chloride, lead sulfate, sodium persulfate, potassium persulfate, ammonium persulfate, ammonium chloride, vanillin, potassium chloride, sodium chloride, lithium nitrate, lithium chloride, lithium carbonate, lithium acetate, lithium triflate, aluminum trifluoromethanesulfonate, aluminum chloride, aluminum nitrate, potassium sulfate, sodium sulfate, ammonium sulfate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, and any mixture thereof.

[0140]

[0144] A thirty-second aspect is the battery of any one of the seventeenth to thirty-first aspects, Negative electrolyte comprises an alkaline electrolyte, the alkaline electrolyte comprising at least one of ammonia, methylamine, glycine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, and any mixture thereof.

[0141]

[0145] A thirty-third aspect is the battery of the thirty-second aspect, wherein the alkaline electrolyte is Negative electrolyte In an amount of 10 to 60% by weight based on the total weight of Negative electrolyte exists within.

[0142]

[0146] A thirty-fourth aspect is the battery of any one of the seventeenth to thirty-third aspects, Negative electrolyte teeth Negative electrolyte Contains additives, Negative electrolyte The additives include at least one of vanillin, indium hydroxide, zinc acetate, zinc oxide, cetyltrimethylammonium bromide, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, polyethylene glycol, ethanol, methanol, zinc gluconate, manganese gluconate, manganese acetate, glucose, and any mixture thereof.

[0143]

[0147] A thirty-fifth aspect is the battery of any one of the seventeenth to thirty-fourth aspects, Positive electrolyte , Negative electrolyte , or both, are gelled or polymerized.

[0144]

[0148] A thirty-sixth embodiment is the battery of any of the second embodiment, in which the separator comprises an ion-selective gel, the ion-selective gel comprising an ionomer, a bipolar membrane, a cation exchange membrane, an anion exchange membrane, an ion-selective grafted cellophane, an ion-selective grafted polyvinyl alcohol, a ceramic separator, NaSiCON, LiSiCON, or any combination thereof.

[0145]

[0149] A thirty-seventh embodiment is the battery of the second embodiment, in which the separator is a gelling layer comprised of an ion-selective ionomer and a buffering agent, the buffering agent comprising potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, or any combination thereof; and the ionomer comprising an acid form of perfluorosulfonic acid (PFSA) / polytetrafluoroethylene (PTFE) copolymer, an anion exchange ionomer with a polyaromatic polymer, or a combination thereof.

[0146]

[0150] A thirty-eighth aspect is the battery of any one of the seventeenth to thirty-seventh aspects, characterized by an average discharge potential of greater than about 1.6V to about 5V.

[0147]

[0151] A thirty-ninth aspect is the battery of any one of the seventeenth to thirty-eighth aspects, characterized by an average discharge potential of about 2V or more to about 5V.

[0148]

[0152] A fortieth aspect is a high voltage metal-free battery comprising: a cathode comprising a cathode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; an anode comprising an anode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; and a catalyst in contact with the cathode, the catalyst being not in contact with the anode and having a pH less than 2. Positive electrolyte and not in contact with the cathode, pH greater than 12, in contact with the anode. Negative electrolyte and, Negative electrolyte and Positive electrolyte and a separator having ion-selective properties disposed therebetween.

[0149]

[0153] A 41st aspect is the battery of the 40th aspect, Positive electrolyte comprises an acidic electrolyte, the acidic electrolyte comprising at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, hydroiodic acid, triflic acid, and any mixture thereof; Positive electrolyte It is present in the blood at a concentration between about 1M and about 16M.

[0150]

[0154] A 42nd aspect is the battery of either the 40th or 41st aspect, Negative electrolyte comprises an alkaline electrolyte, the alkaline electrolyte comprising at least one of ammonia, methylamine, glycine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, and any mixture thereof; Negative electrolyte In an amount of 20 to 60% by weight based on the total weight of Negative electrolyte exists within.

[0151]

[0155] A 43rd aspect is the battery according to any one of the 40th to 42nd aspects, characterized by an average discharge potential of about 2V to about 5V.

[0152]

[0156] A forty-fourth aspect is a method of forming a high voltage metal-free battery, comprising contacting a cathode comprising a cathode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof, with a pH of less than 4. Positive electrolyte and contacting the anode with an anode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof, to achieve a pH greater than 10. Negative electrolyte and not in contact with the cathode. Negative electrolyte and not in contact with the anode Positive electrolyte and disposing at least one of a separator or a buffer layer between the

[0153]

[0157] A 45th aspect is the method of the 44th aspect, Positive electrolyte , Negative electrolyte and disposing the anode, cathode, and separator or buffer layer within a housing to form a high voltage metal-free battery.

[0154]

[0158] A forty-sixth aspect is the method of either of the forty-fourth and forty-fifth aspects, wherein the separator or buffer layer has ion-selective properties.

[0155]

[0159] A 47th aspect is the method of any one of the 44th to 46th aspects, Positive electrolyte comprises an acidic electrolyte, the acidic electrolyte comprising at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, hydroiodic acid, triflic acid, and any mixture thereof, at a concentration between about 1 M and about 16 M. Positive electrolyte exists within.

[0156]

[0160] A 48th aspect is the method of any one of the 44th to 47th aspects, Negative electrolyte comprises an alkaline electrolyte, the alkaline electrolyte comprising at least one of ammonia, methylamine, glycine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, and any mixture thereof; Negative electrolyte In an amount of 20 to 60% by weight based on the total weight of Negative electrolyte exists within.

[0157]

[0161] A forty-ninth aspect is a method of producing energy, wherein a high voltage metal-free battery includes: a cathode including a cathode electroactive material including at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; an anode including an anode electroactive material including at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof, at least a portion of which is oxidized during discharge to form an oxidized anode material; and a cathode in contact with the anode, the anode having a pH less than 4. Positive electrolyte and not in contact with the cathode, pH greater than 10, in contact with the anode. Negative electrolyte and discharging the high voltage metal-free battery to a discharge voltage to produce energy; and charging the high voltage metal-free battery to a charge voltage to reduce at least a portion of the oxidized anode material to an anode electroactive material during charging.

[0158]

[0162] A fiftieth embodiment is the method of the forty-ninth embodiment, wherein the discharge voltage is about 2V or greater.

[0159]

[0163] A 51st aspect is a method according to either of the 49th and 50th aspects, Positive electrolyte comprises an acidic electrolyte, the acidic electrolyte comprising at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, hydroiodic acid, triflic acid, and any mixture thereof, at a concentration between about 1 M and about 16 M. Positive electrolyte exists within.

[0160]

[0164] A 52nd aspect is the method of any one of the 49th to 51st aspects, Negative electrolyte comprises an alkaline electrolyte, the alkaline electrolyte comprising at least one of ammonia, methylamine, glycine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, and any mixture thereof; Negative electrolyte In an amount of 20 to 60% by weight based on the total weight of Negative electrolyte exists within.

[0161]

[0165] Embodiments are described herein with reference to the figures. However, it will be apparent to those skilled in the art that the detailed descriptions provided herein with respect to those figures are for explanatory purposes, as the systems and methods go beyond those limited embodiments. For example, it will be appreciated that those skilled in the art will recognize, in light of the teachings described herein, numerous alternative and suitable approaches, depending on the needs of a particular application, to perform the functionality of any given detail described herein beyond the specific implementation choices in the following embodiments described and shown. That is, there are numerous modifications and variations, too numerous to list, but all falling within the scope of the description herein. Also, singular terms should be construed to include plural terms and vice versa, masculine terms should be construed to include feminine terms and vice versa, and suitable and alternative embodiments do not necessarily imply that the two are mutually exclusive.

[0162]

[0166] It is further understood that the specific methodologies, compounds, materials, manufacturing techniques, uses, and applications described herein may vary, and that the descriptions herein are not limited thereto. It is also understood that the terminology used herein is used only for the purpose of describing particular embodiments, and is not intended to limit the scope of the present systems and methods. As used in this specification and the appended claims (this application or any derivative thereof), it should be noted that the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Thus, for example, a reference to "an element" is a reference to one or more elements and includes equivalents thereof known to those skilled in the art. All conjunctions used should be understood in the most inclusive sense possible. Accordingly, the word "or" should be understood to have the definition of "logical or," not "exclusive or," unless the context clearly dictates otherwise. Structures described herein should also be understood to refer to functional equivalents of such structures. Language that may be interpreted as approximating should be so understood unless the context clearly dictates otherwise.

[0163]

[0167] 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 description belongs. Although any methods, techniques, devices, or materials similar or equivalent to those described herein can be used in the practice or testing of the present systems and methods, the preferred methods, techniques, devices, and materials are described. It should also be understood that structures described herein refer to functional equivalents of such structures. The present systems and methods are described in detail with reference to embodiments thereof, as illustrated in the accompanying drawings.

[0164]

[0168] Other variations and modifications will be apparent to persons skilled in the art from reading the present disclosure, and may involve equivalent and other features that are already known in the art and which may be used instead of or in addition to features already described herein.

[0165]

[0169] Although claims may be formulated to particular combinations of features in this application or any further application derived therefrom, it should be understood that the scope of the present disclosure also includes any novel feature or any novel combination of features explicitly or implicitly disclosed herein, or any generalization thereof, whether or not it relates to the same system or method as presently claimed in any claim, and whether or not it alleviates some or all of the same technical problems as the present system and method.

[0166]

[0170] Features that are described in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment may also be provided separately or in any suitable subcombination. Applicant hereby notifies that new claims may be formulated to such features and / or combinations of such features during prosecution of this application or any further application derived therefrom.

Claims

1. a cathode comprising a cathode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; an anode comprising an anode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; a positive electrolyte not in contact with the anode, having a pH less than 2, and in contact with the cathode; an anode solution not in contact with the cathode, having a pH greater than 10, and in contact with the anode; Including, 1. A high voltage metal-free battery, wherein the cathode solution comprises an acidic electrolyte, the acidic electrolyte being present in the cathode solution at a concentration between about 0.1 M and about 16 M.

2. 10. The battery of claim 1, wherein at least one of the cathode electroactive material or the anode electroactive material does not have a metal in an oxidation state of 0.

3. 10. The battery of claim 1, further comprising a separator disposed between the anode and cathode liquids, the separator having ion-selective properties.

4. 4. The battery of claim 3, wherein the separator comprises an ion-selective gel, the ion-selective gel comprising an ionomer, a bipolar membrane, a cation exchange membrane, an anion exchange membrane, ion-selective grafted cellophane, ion-selective grafted polyvinyl alcohol, a ceramic separator, NaSiCON, LiSiCON, or any combination thereof.

5. 4. The battery of claim 3, wherein the separator is a gelling layer comprised of an ion-selective ionomer and a buffering agent, the buffering agent comprising potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, or any combination thereof, and the ionomer comprising an acid form of perfluorosulfonic acid (PFSA) / polytetrafluoroethylene (PTFE) copolymer, an anion exchange ionomer with a polyaromatic polymer, or a combination thereof.

6. 10. The battery of claim 1, wherein the anode liquid comprises a first gel electrolyte solution and the cathode liquid comprises a second gel electrolyte solution.

7. The cathode electroactive material may be manganese oxide, manganese dioxide (MnO ２ ), Mn ２ O ３ , Mn ３ O ４ , MnO; manganese hydroxide, MnOOH, Mn(OH) ２ Silver oxide, AgO, Ag ２ O; nickel oxide, NiO, Ni ２ O ３ Nickel hydroxide, NiOOH, Ni(OH) ２ Cobalt oxide, Co ３ O ４ , CoO; cobalt hydroxide; lead oxide, PbO, PbO ２ Copper oxide, CuO, Cu ２ O; copper hydroxide; potassium iron oxide (K ２ FeO ４ ); barium iron oxide (BaFeO ４ ); copper hexacyanoferrate; lithium iron phosphate; lithium nickel manganese cobalt oxide; lithium manganese oxide, LiMn ２ O ４ , Li ２ MnO ３ 9,10-anthraquinone; copper sulfide; nickel sulfide; manganese sulfide; tungsten oxide; tin oxide; tin sulfide; tungsten disulfide; vanadium oxide; and any mixture thereof.

8. The anode electroactive material may be manganese oxide, manganese dioxide (MnO ２ ), Mn ２ O ３ , Mn ３ O ４ , MnO; manganese hydroxide, MnOOH, Mn(OH) ２ Silver oxide, AgO, Ag ２ O; nickel oxide, NiO, Ni ２ O ３ Nickel hydroxide, NiOOH, Ni(OH) ２ Cobalt oxide, Co ３ O ４ , CoO; cobalt hydroxide; lead oxide, PbO, PbO ２ Copper oxide, CuO, Cu ２ O; copper hydroxide; potassium iron oxide (K ２ FeO ４ ); barium iron oxide (BaFeO ４ ); copper hexacyanoferrate; lithium iron phosphate; lithium nickel manganese cobalt oxide; lithium manganese oxide, LiMn ２ O ４ , Li ２ MnO ３ 9,10-anthraquinone; copper sulfide; nickel sulfide; manganese sulfide; tungsten oxide; tin oxide; tin sulfide; tungsten disulfide; vanadium oxide; and any mixture thereof.

9. 10. The battery of claim 1, wherein the cathode, the anode, or both comprise conductive carbon mixed with the cathode electroactive material, the anode electroactive material, or both, respectively, comprising graphite, carbon fiber, carbon black, acetylene black, single-walled carbon nanotubes, multi-walled carbon nanotubes, nickel-coated carbon nanotubes, copper-coated carbon nanotubes, dispersions of single-walled carbon nanotubes, dispersions of multi-walled carbon nanotubes, graphene, graphene, graphene oxide, and combinations thereof.

10. 10. The battery of claim 1, wherein the cathode, the anode, or both include an additive and / or dopant, and the additive and / or dopant includes bismuth oxide, copper oxide, indium hydroxide, indium oxide, aluminum oxide, nickel hydroxide, nickel oxide, silver oxide, cobalt oxide, cobalt hydroxide, lead oxide, lead dioxide, quinone, or a combination thereof.

11. 10. The battery of claim 1, wherein the cathode, the anode, or both include a binder, and the binder includes methyl cellulose (MC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPH), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl methyl cellulose (HEMC), carboxymethyl hydroxyethyl cellulose, hydroxyethyl cellulose (HEC), polyvinyl alcohol, TEFLON, or a combination thereof.

12. 10. The battery of claim 1, wherein the cathode, the anode, or both comprise a cathode material pressed onto a current collector, the current collector comprising carbon, lead, nickel, steel, stainless steel, nickel-coated steel, nickel-plated copper, tin-coated steel, copper-plated nickel, silver-coated copper, copper, magnesium, aluminum, tin, iron, platinum, silver, gold, bismuth, titanium, cold-rolled steel, half nickel and half copper, polypropylene, or any combination thereof.

13. 13. The battery of claim 12, wherein the current collector is a foil, a mesh, a perforated foil, a foam, a felt, a fiber, a porous block structure, a honeycomb mesh, a sponge shape, or any combination thereof.

14. 10. The battery of claim 1, wherein the cathode comprises 1 to 99 wt. % cathode electroactive material, 1 to 99 wt. % conductive carbon, 0 to 30 wt. % additives and / or dopants, and 0 to 10 wt. % binder, based on a total weight of the cathode.

15. 10. The battery of claim 1, wherein the anode comprises 1 to 99 wt. % anode electroactive material, 1 to 99 wt. % conductive carbon, 0 to 30 wt. % additives and / or dopants, and 0 to 10 wt. % binder, based on a total weight of the anode.

16. The battery of claim 1, wherein the acidic electrolyte comprises at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, hydroiodic acid, triflic acid, and any mixture thereof.

17. 10. The battery of claim 1, wherein the cathode solution comprises a cathode additive comprising at least one of manganese sulfate, nickel sulfate, potassium permanganate, manganese chloride, manganese acetate, manganese triflate, bismuth chloride, bismuth nitrate, manganese nitrate, nickel sulfate, nickel nitrate, zinc sulfate, zinc chloride, zinc acetate, zinc triflate, indium chloride, copper sulfate, copper chloride, lead sulfate, sodium persulfate, potassium persulfate, ammonium persulfate, ammonium chloride, vanillin, potassium chloride, sodium chloride, lithium nitrate, lithium chloride, lithium carbonate, lithium acetate, lithium triflate, aluminum trifluoromethanesulfonate, aluminum chloride, aluminum nitrate, potassium sulfate, sodium sulfate, ammonium sulfate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, and any mixture thereof.

18. 10. The battery of claim 1, wherein the anode solution comprises an alkaline electrolyte comprising at least one of ammonia, methylamine, glycine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, and any mixture thereof.

19. 20. The battery of claim 18, wherein the alkaline electrolyte is present in the anode solution in an amount of 10 to 60 weight percent, based on the total weight of the anode solution.

20. 10. The battery of claim 1, wherein the anode solution comprises an anode solution additive comprising at least one of vanillin, indium hydroxide, zinc acetate, zinc oxide, cetyltrimethylammonium bromide, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, polyethylene glycol, ethanol, methanol, zinc gluconate, manganese gluconate, manganese acetate, glucose, and any mixture thereof.

21. 10. The battery of claim 1, wherein the positive electrode solution, the negative electrode solution, or both are gelled or polymerized.

22. 10. The battery of claim 1, wherein the battery is characterized by an average discharge potential of greater than about 1.6V to about 5V.

23. 10. The battery of claim 1, wherein the battery is characterized by an average discharge potential of greater than about 2V to about 5V.

24. a cathode comprising a cathode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; an anode comprising an anode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; a positive electrolyte not in contact with the anode and in contact with the cathode, the positive electrolyte having a pH less than 2; an anode solution not in contact with the cathode, having a pH greater than 12, and in contact with the anode; a separator having ion-selective properties and disposed between the anode liquid and the cathode liquid; High voltage metal-free batteries, including:

25. 25. The battery of claim 24, wherein the cathode solution comprises an acidic electrolyte comprising at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, hydroiodic acid, triflic acid, and any mixture thereof, present in the cathode solution at a concentration of between about 1 M and about 16 M.

26. 25. The battery of claim 24, wherein the anode solution comprises an alkaline electrolyte comprising at least one of ammonia, methylamine, glycine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, and any mixture thereof, and is present in the anode solution in an amount of 20 to 60 wt %, based on a total weight of the anode solution.

27. 25. The battery of claim 24, wherein the battery is characterized by an average discharge potential of about 2V to about 5V.

28. 1. A method of forming a high voltage metal-free battery, comprising: placing a cathode solution having a pH less than 4 in contact with a cathode comprising a cathode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; placing an anode solution having a pH greater than 10 in contact with an anode comprising an anode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; disposing at least one of a separator or a buffer layer between the anode and cathode fluid not in contact with the cathode; Including, the positive electrolyte comprises an acidic electrolyte, the acidic electrolyte comprising at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, hydroiodic acid, triflic acid, and any mixture thereof; wherein the acidic electrolyte is present in the cathode solution at a concentration of between about 1 M and about 16 M.

29. 30. The method of claim 28, further comprising disposing the positive electrode, the negative electrode, the anode, the cathode, and the separator or buffer layer in a housing to form a high voltage metal-free battery.

30. 29. The method of claim 28, wherein the separator or buffer layer has ion-selective properties.

31. 29. The method of claim 28, wherein the anode solution comprises an alkaline electrolyte comprising at least one of ammonia, methylamine, glycine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, and any mixture thereof, and is present in the anode solution in an amount of 20 to 60 wt %, based on a total weight of the anode solution.

32. Discharging a high voltage metal-free battery to a discharge voltage to generate energy, the high voltage metal-free battery comprising: a cathode comprising a cathode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; an anode comprising an anode electroactive material comprising at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof, at least a portion of which is oxidized during discharge to form an oxidized anode material; a positive electrolyte not in contact with the anode, having a pH less than 2, and in contact with the cathode; an anode solution not in contact with the cathode, having a pH greater than 10, and in contact with the anode; and charging the high voltage metal-free battery to a charging voltage, reducing at least a portion of the oxidized anode material to the anode electroactive material during charging; 10. A method for generating energy, comprising:

33. 33. The method of claim 32, wherein the discharge voltage is about 2 V or greater.

34. 33. The method of claim 32, wherein the cathode solution comprises an acidic electrolyte comprising at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, hydroiodic acid, triflic acid, and any mixture thereof, and is present in the cathode solution at a concentration of between about 1 M and about 16 M.

35. 33. The method of claim 32, wherein the anode solution comprises an alkaline electrolyte comprising at least one of ammonia, methylamine, glycine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, and any mixture thereof, and is present in the anode solution in an amount of 20 to 60 wt %, based on a total weight of the anode solution.

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