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 Apr. 13, 2020, entitled “Metal - Free High Voltage Battery”, and the entire disclosure thereof is incorporated herein by reference for all purposes.

[0002] Description of Research and Development Sponsored by the Government

[0002] None.

Background Art

[0003]

[0003] Energy storage systems such as batteries are becoming increasingly important in modern society. As countries transition to more green economies, it is becoming standard to combine renewable energy sources with energy storage systems. Batteries are used not only for grid - storage applications but are also increasingly used in many personal electronic devices and electric vehicles. Since the size of the battery (physical and capacity (Ah)) varies depending on the application and the market (e.g., grid, electric vehicle, etc.), due to the close relationship between the battery and the consumer (e.g., personal electronic devices, electric vehicles, etc.), the need for safer, non - toxic, and non - flammable batteries is also changing.

[0004]

[0004] Metal-containing batteries are ubiquitous and have dominated the battery field for over a century, serving several applications for a long time. Some notable examples are zinc, lead, and lithium anode batteries. Silver is used as the cathode. Aluminum and magnesium are gaining momentum as anode materials for future batteries, but currently, these batteries are very unstable and plagued by very low performance. Metals have typically been used as the anode of batteries due to their tendency to lose electrons easily. However, the use of metal electrodes in batteries involves 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 feasible because their electrochemical activity exceeds the stability range of the electrolyte. 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, such organic electrolytes are flammable and sensitive to moisture, making these types of batteries costly to manufacture. The problems with metal anodes such as zinc and lead are the tendency to form gases by separating water and decomposing water to produce hydrogen and oxygen, which can include safety issues. Similar problems are also seen in lithium, aluminum, and magnesium batteries, where lithium, aluminum, and magnesium require expensive and flammable organic electrolytes and a controlled environment for their safe handling.

[0005]

[0005] With respect to rechargeability, metal electrodes tend to form dendrites during repeated cycles, which can lead to separator penetration and battery short - circuit. This depends on the current density applied during battery charging, but nevertheless, it is a problem for all metal anode systems that increases the potential for flammability and explosion. Metal electrodes also tend to passivate by forming oxides or resistive coatings during cycling, which can lead to capacity degradation and eventual battery failure. Other problems include metal corrosion and pitting, which impede long - term rechargeability. There remains a need for batteries that are safe, non - flammable, and non - toxic while exhibiting a relatively wide operating potential window.

Summary of the Invention

[0006]

[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, a separator disposed between and not in contact with the anode and in contact with the cathode Positive electrode solution and not in contact with the cathode and in contact with the anode Negative electrode solution and Negative electrode solution and Positive electrode solution a separator disposed between them. The pH of is less than 4 and the pH of is greater than 10. The separator has ion - selective properties. Positive electrode solution The pH of is less than 4, Negative electrode solution The pH of is greater than 10. The separator has ion - selective properties.

[0007]

[0007] In some embodiments, a method of forming a high - voltage metal - free battery includes disposing in contact with 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 Positive electrode solution and disposing in contact with 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 Negative electrode solutionplacing, and not in contact with the cathode Negative electrode solution and not in contact with the anode Positive electrode solution placing a separator therebetween. Positive electrode solution The pH of is less than 4, Negative electrode solution and the pH of is greater than 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 Description of the Drawings

[0009]

[0009] To more fully understand the present disclosure and its advantages, reference is now made to the following brief description, taken in conjunction with the accompanying drawings in which like reference numerals represent like parts.

[0010]

Figure 1A

[0010] Schematic diagrams of high-voltage metal-free batteries according to some embodiments are shown.

Figure 1B

[0010] Schematic diagrams of high-voltage metal-free batteries according to some embodiments are shown.

Figure 1C

[0010] Schematic diagrams of high-voltage metal-free batteries according to some embodiments are shown.

Figure 1D

[0010] Schematic diagrams of high-voltage metal-free batteries according to some embodiments are shown.

Figure 2

[0011] Graphs of the voltage of the high-voltage metal-free battery over time are shown.

Figure 3

[0012] Discharge curves of the high-voltage metal-free battery compared to a MnO2|Zn battery are shown.

Figure 4

[0013] Discharge capacity curves of the high-voltage metal-free battery are shown.

Figure 5

[0014] Discharge capacity curves of the high-voltage metal-free battery are shown.

BEST MODE FOR CARRYING OUT THE INVENTION

[0011]

[0015] In the present disclosure, the terms “negative electrode” and “anode” are both used to mean “negative electrode”. Similarly, the terms “positive electrode” and “cathode” are both used to mean “positive electrode”. A reference to “electrode” alone may refer to an anode, a cathode, or both. A reference to the term “primary battery” (e.g., “primary battery”, “primary electrochemical cell”, or “primary cell”) refers to a cell or battery that is disposed of and replaced after one discharge. The term “secondary battery” (e.g., “secondary battery”, “secondary electrochemical cell”, or “secondary cell”) refers to a cell or battery that can be recharged and reused one or more times. As used herein, “ Positive electrode solution ” refers to an electrolyte that contacts the cathode without directly contacting the anode, and “ Negative electrode solution ” refers to an electrolyte that contacts the anode without directly contacting the cathode. The term “electrolyte” alone can refer to Positive electrode solution 、 Negative electrode solution 、or an electrolyte that directly contacts both the anode and the cathode.

[0012]

[0016] As used herein, a “metal-free battery” refers to a battery formed without using a metal electroactive material or a metal electrode (i.e., an elemental metal electrode or an alloy metal electrode), and includes a metal-free electrode (e.g., a metal-free electrode may include oxides, hydroxides, sulfides, and salts of other metals). A metal-free battery is also referred to as a metal-free electrode battery. Another non-electroactive component (part of the reaction that generates current), such as a current collector, may contain elemental metal or alloy metal, but the electroactive component of the electrode does not contain elemental metal or alloy metal. Further, as used herein, the term “metal-free electrode” refers to an electrode formed from and including a material other than a metal in an oxidation state of 0. For example, Zn 0(Zn in an oxidation state of 0) may not be a suitable material for forming an electrode in the metal-free battery disclosed herein. However, metals in oxidation states other than 0 can be part of the metal-free electrodes and metal-free batteries disclosed herein, and in some embodiments, the metal-free electrode may be paired with a metal electrode. As another example, Mn 4+ (Mn in an oxidation state of +4) is a suitable material for forming an electrode in the metal-free battery disclosed herein. For example, MnO2 may be used as a cathode material.

[0013]

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

[0014]

[0018] The development of metal-free batteries will solve some of the problems present in metal-based batteries. However, the voltage or potential of a battery depends on both the cathode and the anode, as well as the ability of the anode, which is suitable for metal-based electrodes, to lose electrons. In a single electrolyte system, different metal oxides or sulfides such as manganese dioxide (MnO2),hausmannite (Mn3O4), nickel hydroxide [Ni(OH)2], nickel oxyhydroxide (NiOOH), etc. tend to accept electrons and rather act like cathodes, so they cannot be paired. Furthermore, the voltage generated between these promising electrode active materials is very small.

[0015]

[0019] In this disclosure, a metal-free dual electrolyte battery is disclosed that has a relatively high voltage, a relatively high capacity, and rechargeable characteristics as needed. Non-limiting examples of battery chemistries suitable for use in the present disclosure in metal-free batteries include manganese dioxide (MnO2)|manganese dioxide (MnO2), MnO2|bixbyite (Mn2O3), MnO2|hausmannite (Mn3O4), MnO2|manganese oxide (MnO), MnO2|pyrochlore [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|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 anodes and cathodes of these systems are interchangeable. The use of a dual electrolyte of a highly proton-active electrolyte such as an acid and a highly hydroxyl-active electrolyte such as a base may enable these systems to generate an operating voltage. For example, a battery made with MnO2|MnO2 and a concentrated acid ( Positive electrode solution ) and a base ( Negative electrode solution ) can generate a potential exceeding about 2V. As an example, disclosed herein is the chemistry of a single redox-active element (Mn) in which the oxides are paired in a high-voltage aqueous battery that can be superior in terms of energy (voltage x capacity) and rechargeability to conventional alkaline MnO2 / zinc (Zn) batteries.

{0016}

[0020] In this disclosure, a new battery chemistry including manganese dioxide (MnO2), manganese dioxide (MnO2), MnO2, bixbyite (Mn2O3), MnO2,hausmannite (Mn3O4), MnO2, pyrochloite [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, 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, and a dual electrolyte is employed to create a metal-free battery containing a dual electrolyte, where one of the electrodes is in an electrolyte with high proton activity (e.g., an acid) and the other electrode is in an electrolyte with high hydroxyl activity (e.g., a base). For example, when the battery is based on a chemistry such as MnO2|NiOOH, either electrode can be in an acid or a base, so all of the above chemistry systems (e.g., the new battery chemistry) can function like a cathode and an anode with a positive voltage according to the standard electrochemical reactions in their respective media (e.g., the standard electrochemical reaction in an acidic medium, the standard electrochemical reaction in a basic medium). This separation or isolation of electrolytes with different activities enables the development of some new battery chemistries that were not previously suitable for practical use in batteries, as disclosed herein. The new battery chemistries disclosed herein advantageously develop the manufacture of batteries that are single redox-active elements operating through conversion reactions in a dual electrolyte system. The electrode pairs (e.g., the new battery chemistry) disclosed herein have never been tried or reported in patents or academic literature before.

[0017]

[0021] In this disclosure, the metal-free battery may be based on a single redox-active element (manganese), and its oxides may be paired together as the cathode and anode to produce a high-voltage aqueous battery. In some embodiments, this metal-free battery disclosed herein may be superior in performance to conventional alkaline MnO2|Zn batteries in terms of voltage, capacity, and rechargeability. Non-limiting examples of electrode systems of a single redox-active manganese element and its 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 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, the electrode electroactive materials (e.g., anode electroactive material, cathode electroactive material) suitable for use in the electrodes of the high-voltage metal-free batteries disclosed herein may include manganese dioxide (MnO₂), and the MnO₂ can be any polymorph that occurs in nature or is made in the laboratory. Non-limiting examples of MnO₂ suitable for use in the metal-free electrodes disclosed herein 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 such as pyrolusite, birnessite, bismuth-birnessite, copper-intercalated bismuth birnessite, copper-intercalated birnessite, ramsdellite, hollandite, romanechite, todorokite, lithiophorite, chalcophanite, sodium- or potassium-rich birnessite, cryptomelane, buserite, partially or fully protonated manganese dioxide, lithiumated manganese dioxide, etc., or any combination thereof may also be present in the metal-free electrodes disclosed herein. As disclosed herein, "manganese dioxide (MnO₂)" includes any suitable polymorph that may occur in nature or be made in the laboratory, as well as any mixed oxides and / or minerals containing manganese dioxide such as EMD, α-MnO₂, β-MnO₂, γ-MnO₂, δ-MnO₂, ε-MnO₂, λ-MnO₂, pyrolusite, birnessite, bismuth-birnessite, copper-intercalated bismuth birnessite, copper-intercalated birnessite, ramsdellite, hollandite, romanechite, todorokite, lithiophorite, chalcophanite, sodium- or potassium-rich birnessite, cryptomelane, buserite, partially or fully protonated manganese dioxide, lithiumated manganese dioxide, etc., or any combination thereof. Without wishing to be bound by theory, the mechanism by which a battery such as MnO₂|MnO₂ operates is by solid proton insertion and dissolution-precipitation reactions in both acidic and basic electrolytes.MnO2 in acidic media tends to form electrolytic manganese dioxide or γ-MnO2 during charging through one or two of its electron reactions, while MnO2 in basic electrolytes converts itself to δ-MnO2 during charging after successive one or two electron reactions. γ-MnO2 undergoes solid proton insertion for its first electron reaction and a dissolution-precipitation reaction for its second electron reaction in both media, but γ-MnO2 in basic electrolytes is ultimately converted to δ-MnO2. γ-MnO2 in acidic media can undergo a direct dissolution-precipitation reaction depending on the strength of the acid used. Thus, by creating γ-MnO2|γ-MnO2 and γ-MnO2|δ-MnO2 batteries, it can operate through a wide range of chemical reactions. The γ-MnO2|Mn3O4 battery can have γ-MnO2 operating in acidic electrolytes while Mn3O4 operates in alkaline electrolytes, and the operation of this battery can involve exchanging the electrolyte, for example, γ-MnO2 in base and Mn3O4 in acid. In the case of γ-MnO2 in acid, depending on the strength of the acid, it can undergo proton insertion and dissolution precipitation, or dissolution precipitation followed by, but Mn3O4 directly follows a dissolution-precipitation reaction.

[0019]

[0023] The rechargeable characteristics of the metal-free batteries disclosed herein can be obtained by adding dopants or additives to the electrodes and / or electrolytes. In some embodiments, the electrode additives can help enhance the rechargeability of the metal-free batteries disclosed herein. Irrespective 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 material and the anode material. Non-limiting examples of electrode additives suitable for use in the metal-free electrodes of the present disclosure 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 various pHs can be important to prevent the occurrence of neutralization reactions. In some embodiments, the separation of electrolytes can be achieved by gelling the electrolytes, which physically prevents the mixing of the electrolytes. The use of cross-linking agents and ionomers in the gelling process anticipates the use of cellulose-based separators such as cellophane, or polymer-based separators such as polyvinyl alcohol or cross-linked polyvinyl alcohol, and can also prevent ion crossover. The electrolyte gelling process can be carried out using a free radical polymerization process. Acrylamide and acrylic acid can form long polymer chains by mixing with electrolytes having high proton activity or high hydroxyl activity. Cross-linking agents such as N,N'-methylenebisacrylamide (MBA) can be used to increase the strength of the polymer, increase the viscosity, and impart self-healing properties. The gelling or polymerization of the electrolyte can be carried out using initiators such as potassium persulfate or sodium persulfate or ammonium persulfate. In some embodiments, preventing the mixing of electrolytes can be achieved by using ion-selective ceramic separators or membranes such as LiSiCON, NaSiCON, Nafion membranes, anion exchange membranes, bipolar membranes, or any combination thereof.

[0021]

[0025] On the cathode side Positive electrode solution has a relatively high proton activity, and on the anode side Negative electrode solution has a relatively high hydroxyl activity. The advantage of having a dual electrolyte cell is an increase in the cell potential. The relatively high proton activity on the cathode side and the relatively high hydroxyl activity on the anode side can increase the cell potential, which can then lead to a higher average discharge voltage and higher energy from the cell.

[0022]

[0026] Another advantage of separating the electrolytes used in the cathode and anode is to generate the positive voltage and cycle performance of the novel battery chemistries disclosed herein. Generally, an acid is preferred for the cathode and a base is preferred for the anode. The electrolyte can exchange between the cathode and the 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, hydrobromic acid, hydroiodic acid, trifluoro 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 the performance of the battery. 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 trifluoro acid, bismuth chloride, bismuth nitrate, manganese nitrate, nickel sulfate, nickel nitrate, zinc sulfate, zinc chloride, zinc acetate, zinc trifluoro acid, indium chloride, copper sulfate, copper chloride, lead sulfate, sodium persulfate, potassium persulfate, ammonium persulfate, ammonium chloride, vanillin, sodium hypophosphite, potassium chloride, sodium chloride, or any combination thereof.

[0024]

[0028] In some embodiments, the electrolyte can be gelled with a corresponding additive that physically separates the electrolyte and helps prevent neutralization of the electrolyte. Gelation or polymerization of the electrolyte can be performed by various techniques such as via free radical polymerization. Acrylamide and acrylic acid can form long polymer chains by mixing with electrolytes having relatively high proton activity or relatively high hydroxyl activity. Cross-linking agents such as MBA can be used to increase the strength of the polymer, make the polymer more viscous, and impart self-healing properties to the polymer. Gelation or polymerization can be performed using initiators such as potassium persulfate or sodium persulfate or ammonium persulfate.

[0025]

[0029] Separation of the electrolyte can be achieved by using any suitable methodology. For example, a gel layer embedded with an ionomer having ion-selective properties can function as a barrier layer to prevent crossover of neutralizing ions. The gelation procedure can be performed via free radical polymerization disclosed herein. Buffer additives that 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 a dual electrolyte to generate high voltage and capacitance of the corresponding electrodes. For the first time, a novel electrode pair is presented, and such an electrode pair advantageously exhibits additional battery advantages of safety, non-toxicity, and non-flammability. For the first time in patent and academic literature, a pair of single redox-active elements is disclosed, and this novel pair of electrode chemistries exhibits the conversion properties of a dual electrolyte that advantageously increases the energy density of the battery.

[0027]

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

[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 above 1.6V and 5V. The average discharge potential of a conventional alkaline MnO2|Zn battery is 1.6V. The high-voltage metal-free battery disclosed herein may be single-use or may have 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 may be rechargeable. The electrode pairs of this system may be of a single redox-active element's oxide, hydroxide, oxyhydroxide, sulfide, organic compound, or any combination thereof, and / or 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, respectively, during charging and discharging. Without wishing to be bound by theory, the resulting capacity may be due to the mechanism of ion insertion or intercalation and / or dissolution-precipitation reactions. The relatively high discharge potential can be achieved by the separation of electrolytes having various strengths with respect to hydrogen (or proton) activity and hydroxyl activity. In some embodiments, the long-term rechargeability of the high-voltage metal-free battery can be obtained by the use of additives and / or dopants. Negative electrode solution and Positive electrode solution separation can also be obtained by the use of ion-selective ceramic and / or polymer membranes. In some cases, separation can be achieved by the use of gelling of the electrolyte embedded with an ion-selective ionomer to prevent neutralization by ion migration. Further, a gelling separator that functions as a buffer layer containing an ion-selective ionomer and a buffer Negative electrode solution to Positive electrode solutionmay be employed for separation. Non-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, a high-voltage metal-free battery may have any geometric form factor, as needed. To those skilled in the art, a high-voltage aqueous Zn anode battery may be cylindrical or prismatic. Further, the high-voltage metal-free battery may be flexible as needed, by gelling the electrolyte and electrodes, or by using binders within the electrodes that allow for flexibility.

[0030]

[0034] Referring to FIGS. 1A through 1D, battery 10 may include a housing 7, a cathode 12 that may include a cathode current collector 1 and a cathode material 2, and an anode 13. In some embodiments, anode 13 may include an anode current collector 4 and an anode material 5. Note that the scales of the components in FIGS. 1A through 1D are not to scale and are characterized to clearly show the electrolyte around anode 13 and cathode 12. FIGS. 1A through 1C show a prismatic battery configuration having a single anode 13 and cathode 12. In another embodiment, the battery may be a cylindrical battery (such as shown in FIG. 1D) in a rolled configuration having concentrically arranged electrodes, or in a rolled configuration where the anode and cathode are layered and then rolled to form a jelly roll configuration. Cathode current collector 1 and cathode material 2 are collectively referred to as cathode 12 or positive electrode 12, as shown in FIG. 1D. Similarly, anode material 5 with optional anode current collector 4 may be collectively referred to as anode 13 or negative electrode 13. The electrolyte may contact cathode 12 and anode 13. As described in more detail herein, the electrolyte contacting 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 characteristics of battery 10 in some embodiments.

[0031]

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

[0032]

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

[0033]

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

[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, even if metal is present in the electrodes or other parts of the battery, the electroactive material of each electrode may not contain metal. The pair of cathode 12 and anode 13 may be any combination of the electrode materials disclosed herein, which may be present as organic compounds, oxides, hydroxides, oxyhydroxides, and / or sulfides.

[0035]

[0039] Suitable electrode materials (e.g., cathode material 2, anode material 5) include, but are not limited to, manganese dioxide, copper manganese oxide,hausmannite, manganese oxide, copper intercalated bismuth vermiculite, vermiculite, todorokite, ramsdellite, pyrolusite, pyrochlore, 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 (α and β), 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 oxides, Mn3O4, heterolite (ZnMn2O4), 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, nitroxide-oxoammonium cation redox pairs 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 oxophosphate, or any combination thereof. In some embodiments, the cathode may include an air electrode.

[0036]

[0040] In some embodiments, the electrode material (e.g., cathode material 2, anode material 5) can be based on one or more polymorphic MnO2 including electrolytic manganese dioxide (EMD), α-MnO2, β-MnO2, γ-MnO2, δ-MnO2, ε-MnO2, or λ-MnO2. Hydrated MnO2, pyrolusite, birnessite, ramsdellite, hollandite, romanechite, todorokite, lithiophorite, chalcophanite, sodium- or potassium-rich birnessite, cryptomelane, buserite, manganese oxyhydroxide (MnOOH), α-MnOOH, γ-MnOOH, β-MnOOH, manganese hydroxide [Mn(OH)2], partially or fully protonated manganese dioxide, Mn3O4, Mn2O3, bixbyite, MnO, lithiated manganese dioxide (LiMn2O4, Li2MnO3), CuMn2O4, 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 may also be present. Generally, the cyclic form of manganese dioxide in the electrode can have a layered structure that can include δ-MnO2, which in some embodiments is referred to in much the same sense as birnessite. When non-birnessite polymorphic forms of manganese dioxide are used, they can be converted in-situ to birnessite by one or more state conditioning cycles described in more detail below. For example, a complete or partial discharge (e.g., between about 20% and about 100% of the second electron capacity of the cathode) is performed until the end of the second electron stage of MnO2, followed by recharging to that Mn 4+ state, resulting in manganese dioxide in the birnessite phase.

[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 MnO2 such as pyrolusite, birnessite, ramsdellite, hollandite, romanechite, todorokite, lithiophorite, chalcophanite, sodium- or potassium-rich birnessite, cryptomelane, buserite, manganese oxyhydroxide (MnOOH), α-MnOOH, γ-MnOOH, β-MnOOH, manganese hydroxide [Mn(OH)2], partially or fully protonated manganese dioxide, Mn3O4, Mn2O3, bixbyite, MnO, lithiated manganese dioxide (LiMn2O4), CuMn2O4, zinc manganese dioxide, or any combination thereof may also be present in the electrode material.Non-limiting examples of electrode materials (e.g., cathode material 2, anode material 5) suitable for use in the high-voltage metal-free battery disclosed herein include electrolytic manganese dioxide (EMD), α-MnO2, β-MnO2, γ-MnO2, δ-MnO2, ε-MnO2, λ-MnO2, pyrolusite, birnessite, ramsdellite, hollandite, romanechite, todorokite, lithiophorite, chalcophanite, sodium- or potassium-rich birnessite, cryptomelane, buserite, manganese oxyhydroxide (MnOOH), α-MnOOH, γ-MnOOH, β-MnOOH, manganese hydroxide [Mn(OH)2], partially or fully protonated manganese dioxide, Mn3O4, Mn2O3, bixbyite, 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 can be formed by pairing any of the cathode materials described herein with any of the anode materials described above in the presence of a suitable electrolyte (e.g., suitable Negative electrode solution and Positive electrode solution etc.) such that a voltage can be generated.

[0039]

[0043] In some embodiments, the cathode 12 used in the high-voltage metal-free battery disclosed herein may include an electroactive material having electrochemical activity in an electrolyte with high proton activity, such as metal oxides, metal hydroxides, metal oxyhydroxides, metal salts (e.g., metal sulfides), organic compounds, etc. Positive electrode solution It may include an electroactive material having electrochemical activity in an electrolyte with high proton activity, such as in 3.

[0040]

[0044] In some embodiments, the anode 13 used in the high-voltage metal-free battery disclosed herein may include an electroactive material having electrochemical activity in an electrolyte with high hydroxyl activity, such as metal oxides, metal hydroxides, metal oxyhydroxides, metal salts (e.g., metal sulfides), organic compounds, etc. Negative electrode solution It may include an electroactive material having electrochemical activity in an electrolyte with high hydroxyl activity, such as in 6.

[0041]

[0045] Non-limiting examples of electrode materials (e.g., cathode material 2, anode material 5) having electrochemical activity in electrolytes with high proton activity or high hydroxyl activity 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 are pyrolusite, birnessite, ramsdellite, hollandite, romanechite, 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, bixbyite, MnO, lithiumated manganese dioxide (LiMn2O4), CuMn2O4, zinc manganese dioxide, lead oxide, lead, 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, etc., may also be present in the electrodes (e.g., cathode 12, anode 13). Combinations of electroactive materials may also be employed as electrode materials (e.g., cathode material 2, anode material 5). The electroactive electrode materials (e.g., electroactive cathode material 2, electroactive anode material 5) can 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 battery disclosed in this specification include manganese dioxide (MnO2)|manganese dioxide (MnO2), MnO2|bixbyite (Mn2O3), MnO2|hausmannite (Mn3O4), MnO2|pyrochloite [Mn(OH)2], MnO2|manganese oxyhydroxide (MnOOH), MnO2|manganese oxide (MnO), 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|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. MnO2, NiOOH, etc. can exist in various polymorphic forms when paired in these battery systems.

[0043]

[0047] The cathode electroactive material and / or the anode electroactive material may need to be mixed with a conductive additive such as carbon. By adding a conductive additive such as conductive carbon, it becomes possible to highly fill the electroactive material in the electrode material (for example, cathode material 2, anode material 5), and as a result, the volume and weight energy densities increase. In some embodiments, the conductive additive may be present in the electrode material (for example, cathode material 2, anode material 5) in an amount of about 1 to 30% by weight based on the total weight of the electrode material (for example, 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, a dispersion of single-walled carbon nanotubes, a dispersion of multi-walled carbon nanotubes, graphene, graphyne, graphene oxide, or a combination thereof. The higher filling of the electroactive material of the electrode (for example, cathode 12, anode 13) is desirable in some embodiments to increase the energy density. Other examples of conductive carbon include TIMREX primary synthetic graphite (all types), TIMREX natural flake graphite (all types), TIMREX MB, MK, MX, KC, B, LB grades (by way of example, 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 (by way of example, Ketjenblack EC-300J, Ketjenblack EC-600JD, powder of Ketjenblack EC-600JD), acetylene black, carbon nanotubes (single-walled or multi-walled), Zenyatta graphite, and / or a combination thereof.

[0044]

[0048] In some embodiments, the particle size range of the conductive additive can be from 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 in the tens to hundreds of nanometers. In some embodiments, the mass ratio of graphite to the conductive additive can range from about 5:1 to about 50:1, or from about 7:1 to about 28:1. The total mass percentage (e.g., the total mass percentage of carbon) of the conductive additive in the electrode material (e.g., cathode material 2, anode material 5) can range from about 5% to about 99%, or from 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 the electrode materials (e.g., cathode material 2, anode material 5) to improve rechargeability and performance. The additive can be in the form of a powder mixed with the electroactive material or in the form of a substrate to which the electroactive and conductive carbon can be attached. Non-limiting examples of additives suitable for use in the 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, quinone, their salts, their derivatives, or any combination thereof. In some embodiments, the dopant or additive can be present in the electrode materials (e.g., cathode material 2, anode material 5) in an amount between 0 and 30 wt% based on the total weight of the electrode materials (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. The 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 wt%. 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, salt powder, 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 function as a supporting conductive skeleton for the first and second electron reactions to occur. The second electron reaction has a dissolution-precipitation reaction in which Mn 3+ ions dissolve in the electrolyte and precipitate on a material such as graphite, resulting in an electrochemical reaction and the formation of non-conductive manganese hydroxide [Mn(OH)2]. This ultimately leads to a capacity decrease 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, Ti, and / or oxides, salts, and / or hydroxides of metals such as Ag, Au, Al, Ca. Oxides, salts, and / or hydroxides of transition metals such as Co also include Mn 3+It may be useful to reduce the solubility of ions. Such conductive components may be incorporated into electrodes (e.g., cathode 12, anode 13) by chemical means or physical means (e.g., ball mill, mortar / pestle, Spex mixer). Examples of such electrodes (e.g., cathode 12, anode 13) include 5 to 95% of birnessite, 5 to 95% of conductive carbon, 0 to 50% of conductive components, and 1 to 10% of a binder.

[0047]

[0051] In some embodiments, the binder can be used with electrode materials (e.g., cathode material 2, anode material 5). The binder can be present at a concentration between about 0 to 10 wt% or between about 1 to 5 wt% of the weight of the electrode material (e.g., cathode material 2, anode material 5). In some embodiments, the binder can be used as a thickener and a strong binder and includes a water-soluble cellulose-based hydrogel cross-linked with a conductive polymer with good mechanical strength. The binder can be a cellulose film sold as cellophane. The binder can be created by physically cross-linking a water-soluble cellulose-based hydrogel with a polymer by repeating cycles of cooling and thawing. In some embodiments, the binder can include a 0 to 10 wt% carboxymethyl cellulose (CMC) solution cross-linked with 0 to 10 wt% polyvinyl alcohol (PVA) based on equal volume. The binder exhibits excellent performance compared to conventionally used TEFLON® or PTFE (polytetrafluoroethylene). TEFLON® or PTFE is a high-resistance material but is widely used in the industry due to its excellent rollability. However, this does not exclude the use of TEFLON® or PTFE as a binder. A mixture of TEFLON® or PTFE with an aqueous binder and some conductive carbon can be used to create a rollable binder. The use of an aqueous binder can help achieve a significant portion of the two-electron capacity while minimizing capacity loss over many cycles. In some embodiments, the binder can be aqueous, have excellent water retention and adhesion properties, and help maintain conductivity compared to the same cathode using a PTFE binder instead. Examples of suitable aqueous 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, polyvinyl pyrrolidone, polyvinylidene fluoride, polypyrrole, and combinations thereof. In some embodiments, a 0 to 10 wt% solution of aqueous cellulose hydrogen can be crosslinked with a 0 to 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 may be mixed with 0 to 5% PTFE to improve manufacturability.

[0048]

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

[0049]

[0053] The bismuth compound can be incorporated into the cathode 12 as an inorganic or organic salt of bismuth (in an oxidation state of 5, 4, 3, 2, or 1), or as bismuth oxide. The bismuth compound can be present in the electrode material (e.g., cathode material 2, anode material 5) at a concentration between about 1 to 20 wt% 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, bismuth oxychloride, bismuth aluminate hydrate, bismuth tungsten oxide, bismuth lead strontium calcium copper oxide, bismuth antimonide, bismuth telluride antimonide, yttria-stabilized bismuth oxide (e.g., yttria-doped bismuth oxide), bismuth-lead alloy, bismuth ammonium citrate, 2-naphthol bismuth salt, dichloro(tri-o-tolyl)bismuth, dichlorodiphenyl(p-tolyl)bismuth, triphenylbismuth, and / or combinations thereof.

[0050]

[0054] The copper compound can 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 can be present at a concentration between about 1% and 70% by weight of the weight of the electrode material (e.g., cathode material 2, anode material 5). In some embodiments, the copper compound is present at a concentration between about 5% and 50% by weight of the weight of the electrode material (e.g., cathode material 2, anode material 5). In other embodiments, the copper compound is present at a concentration between about 10% and 50% by weight of the weight of the electrode material (e.g., cathode material 2, anode material 5). In still other embodiments, the copper compound is present at a concentration between about 5% and 20% by weight 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 of +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 voltages of the bismuth compound. This results in an electrode (e.g., cathode 12, anode 13) having complete reversibility during constant current cycling, as compared to bismuth-modified MnO2 which cannot withstand constant current cycling.

[0051]

[0055] The electrodes (e.g., cathode 12, anode 13) can be manufactured using methods that are feasible for large-scale production. In some embodiments, the electrode materials (e.g., cathode material 2, anode material 5) can include 2 to 30 wt% of conductive carbon, 0 to 30 wt% of conductive additive, 1 to 70 wt% of copper compound, 1 to 20 wt% of bismuth compound, 0 to 10 wt% of binder, and vernadite or EMD. In another embodiment, the electrode materials (e.g., cathode material 2, anode material 5) include 2 to 30 wt% of conductive carbon, 0 to 30 wt% of conductive additive, 1 to 20 wt% of bismuth compound, 0 to 10 wt% of binder, and vernadite or EMD. In one embodiment, the electrode materials (e.g., cathode material 2, anode material 5) are mainly composed of 2 to 30 wt% of conductive carbon, 0 to 30 wt% of conductive additive, 1 to 70 wt% of copper compound, 1 to 20 wt% of bismuth compound, 0 to 10 wt% of binder, and the balance is vernadite or EMD. In another embodiment, the electrode materials (e.g., cathode material 2, anode material 5) are mainly composed of 2 to 30 wt% of conductive carbon, 0 to 30 wt% of conductive additive, 1 to 20 wt% of bismuth compound, 0 to 10 wt% of binder, and the balance is vernadite 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. The porosity can be measured in accordance with ASTM D4284-12, "Standard Test Method for Measuring Pore Volume Distribution of Catalysts and Catalyst Carriers by Mercury Intrusion Porosimetry," using the version current as of the filing date of this application.

[0053]

[0057] An electrode material (e.g., cathode material 2, anode material 5) can be formed on an electrode current collector (e.g., cathode current collector 1, anode current collector 4) formed from a conductive material that serves as an electrical connection between the electrode material (e.g., cathode material 2, anode material 5) and an external electrical connection. As described herein, the current collector can be a metal in some embodiments. Since the current collector is not an electroactive material, the battery can be called a metal-free battery even when the current collector contains a metal. In some embodiments, the electrode current collector (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 collector (e.g., cathode current collector 1, anode current collector 4) can include carbon felt, carbon foam, a conductive polymer mesh, or any combination thereof. The electrode current collector (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 collector (e.g., cathode current collector 1, anode current collector 4) can be formed as, or a part of, a pocket assembly in which the pockets can hold the electrode material (e.g., cathode material 2, anode material 5) within the electrode current collector (e.g., cathode current collector 1, anode current collector 4, respectively). A tab can be coupled to the current collector to provide an electrical connection between the external power source and the current collector. As shown at the top of the electrodes (e.g., cathode 12, anode 13) in FIG. 1B, the tab can be a part of the electrode current collector (e.g., cathode current collector 1, anode current collector 4) that extends outside the electrode material (e.g., cathode material 2, anode material 5, respectively).

[0054]

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

[0055]

[0059] In some embodiments, the cathode material and the anode material having corresponding electroactive materials can also be formed from dissolved salts in the corresponding electrolyte (e.g., Positive electrode solution and Negative electrode solution ), respectively). The process of forming the cathode material and the anode material from the dissolved salts in the corresponding electrolyte includes a charging step or a forming step in which the dissolved salt containing active ions is plated onto the current collector by electrons flowing in from an external circuit. For example, manganese salts such as manganese sulfate and manganese triflate in an electrolyte with high proton activity electroplate MnO2 during the charging or forming step.

[0056]

[0060] As shown in FIG. 1B, the battery 10 may not include a separator. The ability to form the battery 10 without a separator can reduce the overall cost of the battery while having the same or similar performance as a battery with a separator. Positive electrode solution and Negative electrode solution The use of a polymer gel electrolyte (PGE) for

[0057]

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

[0058]

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

[0059]

[0063] Separator 9 may include various materials. If there are one or more separators, the use of PGE with respect to the electrolyte may enable the use of a relatively inexpensive separator 9. For example, separator 9 may include CELLOPHANE®, polyvinyl alcohol, CELGARD®, a composite of polyvinyl alcohol and graphene oxide, cross-linked polyvinyl alcohol, PELLON®, and / or a composite of carbon - polyvinyl alcohol. The use of separator 9 may help improve the cycle life of battery 20, but is not essential in all embodiments.

[0060]

[0064] When a buffer layer is used, the buffer layer may be used alone or in combination with separator 9. The buffer layer Negative electrode solution and / or Positive electrode solution may include a gelled solution having the same electrolyte formulation as. For example, the buffer layer may be the PGE described herein. One or more additives such as calcium hydroxide, layered double hydroxides such as hydrotalcites, quintinite, forgellite, magnesium hydroxide, or combinations thereof may also be present in the buffer layer. For example, Negative electrode solution and Positive electrode solution are substantially the same formulation, and only the composition of protons and hydroxyl anions, and / or the viscosity is different, the concentration of the electrolyte in the buffer layer may be Negative electrode solution or Positive electrode solution the same as, or Negative electrode solution between the concentration of and Positive electrode solution the concentration of. The buffer layer Negative electrode solution and Positive electrode solution of course limits the movement of ions between, Negative electrode solution and Positive electrode solution and helps prevent mixing between, Negative electrode solution or Positive electrode solution may have a higher viscosity than either.

[0061]

[0065] As shown in FIGS. 1A through 1D, Positive electrode solution 3 may contact cathode 12, Negative electrode solution 6 may contact anode 13. As described in more detail herein,Positive electrode solution One or both of 3 and / or Negative electrode solution 6 may be polymerized or gelled to form a separate gel electrolyte in order to prevent mixing between the two electrolyte solutions. Positive electrode solution 3 may be disposed within the housing 10 in contact with the cathode material 2. In some embodiments, Negative electrode solution 6 may be polymerized or gelled, Positive electrode solution 3 may be liquid. In another embodiment, Positive electrode solution 3 may be polymerized or gelled, Negative electrode solution 6 may be liquid. Negative electrode solution The polymerization of 6, Positive electrode solution even when 3 is liquid, Positive electrode solution between 3 and Negative electrode solution 6 can be prevented. Positive electrode solution The polymerization of 3, Negative electrode solution even when 6 is liquid, Positive electrode solution between 3 and Negative electrode solution 6 can be prevented. In some embodiments, Positive electrode solution both 3 and Negative electrode solution 6 are gelled.

[0062]

[0066] As disclosed herein, the electrolytes on the cathode side and the anode side will be separated. For the cathode electrolyte (e.g., Positive electrode solution 3), an acid is usually preferred, and for the anode electrolyte (e.g., Negative electrode solution 6), a base is usually preferred. However, the electrolytes can be easily exchanged between the two electrodes as needed. Non-limiting examples of acids suitable for use in the electrolytes disclosed herein (e.g., Positive electrode solution 3, Negative electrode solution 6) include hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, triflic acid, or any combination thereof. Triflic acid is a superacid with high proton activity, and the use of these acids helps to significantly improve the performance. Non-limiting examples of acids suitable for use in the electrolytes disclosed herein (e.g., Positive electrode solution 3, Negative electrode solutionNon-limiting examples of bases suitable for use in 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] An acidic electrolyte (e.g., Positive electrode solution 3, Negative electrode solution 6) has a relatively high proton activity that defines the potential of the battery. The higher the activity of protons in the electrolyte, the higher the potential of the battery. The acid dissociation constant (K a ) is a relatively good indicator for judging the activity of protons. Non-limiting examples of acidic electrolytes or ions suitable for use in (e.g., Positive electrode solution 3, Negative electrode solution 6) with K a ranging from low to very large include hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, triflic acid, or any combination thereof. In some embodiments, Positive electrode solution 3 contains an acidic electrolyte.

[0064]

[0068] An electrolyte (e.g., Positive electrode solution 3, Negative electrode solution 6) can be an acidic solution whose pH can be less than about 4, or less than about 3, or less than about 2, or less than about 1, or between -1.2 and 4, or between -1.2 and 3, or between -1.2 and 2, or between -1.2 and 1. The electrolyte solution (e.g., Positive electrode solution 3, Negative electrode solution 6) can be used under temperature conditions in the range between 0°C and 200°C. In some embodiments, the electrolyte (e.g., Positive electrode solution 3, Negative electrode solution6) may contain 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, or about 0.001 M to about 16 M, or about 0.01 M to about 16 M, or about 0.1 M to about 16 M, or about 1 M to about 16 M.

[0065]

[0069] In some embodiments, the acidic electrolyte (e.g., Positive electrode solution 3, Negative electrode solution 6) hydrogen activity can be altered by using acids of different strengths. K a is a relatively good indicator for judging the strength of an acid. For electrolyte solutions, the following electrolytes or ions can be used, ranging from those with low K a to those with very high values: hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, trifluoro acid, or any combination thereof. These examples of acidic electrolytes can help in altering the hydrogen (or proton) activity, but it will be apparent to those skilled in chemistry or electrochemistry that any combination of acidic electrolytes with other electrolytes can be used to alter the proton activity.

[0066]

[0070] The alkaline electrolyte (e.g., Positive electrode solution 3, Negative electrode solution 6) has a relatively high hydroxyl activity that defines the potential of the battery. The higher the activity of hydroxyl in the electrolyte, the higher the potential of the battery. Non-limiting examples of alkaline electrolytes or ions with relatively high hydroxyl activity suitable for use in the electrolyte (e.g., Positive electrode solution 3, Negative electrode solution 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. In some embodiments, Negative electrode solution 6 contains a basic electrolyte (e.g., an alkaline electrolyte).

[0067]

[0071] In some embodiments, Negative electrode solution it can be an alkaline electrolyte (e.g., an electrolyte solution with relatively high alkalinity), Positive electrode solution or it can be an acidic solution (e.g., a solution with relatively high acidity).

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

[0069]

[0073] In some embodiments, the hydroxyl activity of the electrolyte (e.g., Positive electrode solution 3, Negative electrode solution 6) can be changed by using bases of different strengths, and can be used from the following low-strength ones to high-strength ones: ammonia, methylamine, glycine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, or any combination thereof. These examples of alkaline electrolytes may be useful for changing the hydroxyl activity, but it will be apparent to those skilled in the art of chemistry or electrochemistry that any combination of alkaline electrolytes and other electrolytes can be used to change the hydroxyl activity.

[0070]

[0074] Electrolyte additives can be useful for improving the performance of the cathode material and the anode material. The acidic electrolytes disclosed herein (e.g., acidic cathode electrolytes, Positive electrode solutionNon-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 0 M and 5 M. The basic electrolytes disclosed herein (e.g., alkaline anode electrolytes, Negative electrode solution 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 electrode solution 3) The additive can help improve the performance of the electrode material (e.g., the cathode material). Acidic electrolyte additives suitable for use in the present disclosure (e.g., Positive electrode solutionNon-limiting examples of the 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 electrode solution The concentration of the additive can be between 0 M and 5 M.

[0072]

[0076] In some embodiments, the acidic electrolyte solution (e.g., the cathode solution) may include a solution containing 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, potassium sulfate, cobalt sulfate, lead sulfate, sodium hydroxide, potassium hydroxide, titanium sulfate, titanium chloride, lithium nitrate, lithium chloride, lithium bromide, lithium bicarbonate, lithium acetate, lithium sulfate, lithium nitrate, lithium nitrite, lithium hydroxide, lithium perchlorate, lithium oxalate, lithium fluoride, lithium carbonate, lithium sulfate, lithium bromate, polyvinyl alcohol, carboxymethyl cellulose, xanthan gum, carrageenan, acrylamide, potassium persulfate, sodium persulfate, ammonium persulfate, N,N'-methylenebisacrylamide, or any combination thereof. For example, the cathode 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 cathode solution may include manganese sulfate, ammonium chloride, ammonium sulfate, manganese acetate, potassium permanganate, and / or a salt of permanganate, and the concentration of the additive may be between 0M and 10M. Depending on the type of manganese salt used, the voltage of the battery system may vary. For example, in a manganese sulfate electrolyte, the voltage of the SS-HiVAB is about 2.45 - 2.5V, while in a potassium permanganate electrolyte, the voltage of the SS-HiVAB is about 2.8 - 2.9V.

[0073]

[0077] In some embodiments, the acidic electrolyte (e.g., Positive electrode solution(3) may contain permanganate. Permanganate has a high positive potential. This can enable an increase in the overall cell potential within the battery 10. When present, the amount of permanganate can vary based on the expected operating conditions of the battery 10, but it can be present in a molar ratio of acid (e.g., mineral acids such as hydrochloric acid, sulfuric acid, etc.) to permanganate of about 5:1 to about 1:5, or about 1:1 to about 1:6, or between about 1:2 and about 1:4, or about 1:3. The concentration of permanganate (e.g., potassium permanganate or salts of permanganate) can be greater than 0 and less than or equal to 5M. In some embodiments, the acidic electrolyte solution (e.g., the 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 for creating high-voltage batteries. Positive electrode solution When it contains permanganate, suitable permanganates can include, but are not limited to, potassium permanganate, sodium permanganate, lithium permanganate, calcium permanganate, and combinations thereof.

[0074]

[0078] In addition to the hydroxide, the alkaline electrolyte (e.g., Negative electrode solution (6) may contain additional components. In some embodiments, the alkaline electrolyte can have zinc oxide, potassium carbonate, potassium iodide, and potassium fluoride as additives. When a zinc compound is Negative electrode solution present therein, Negative electrode solution can 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, the alkaline electrolyte (e.g., Negative electrode solution 6) may include electrolyte additives such as 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 (e.g., Negative electrode solution 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, chain carbonates, dialkyl carbonates, aliphatic carboxylic acid esters, γ-lactones, chain ethers, cyclic ethers, aprotic organic solvents, fluorinated carboxylic acid esters, and combinations thereof. Any suitable additives containing the salts described herein can be Negative electrode solution and / or Positive electrode solution used with the organic solvent to form an organic electrolyte for use.

[0077]

[0081] In some embodiments, the ionic liquid is a gel electrolyte (e.g., gelled Negative electrode solution , gelled Positive electrode solutioncan be used to form, etc. Ionic liquids include 1-ethyl-3-methylimidazolium chloride (EMImCl), 1-allyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium chloride, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium tetrachloroaluminate, lithium hexafluorophosphate (LiPF6), lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(oxalato)borate, and combinations thereof. Other ionic liquids are known and can also be used. In some embodiments, EMImCl can be used as an ionic liquid and can be purified before being mixed with an aluminum salt to form an aluminum ion-conductive electrolyte. The aluminum salt can be aluminum chloride, aluminum acetate, aluminum nitrate, aluminum bromide, etc. A mixture of EMImCl and aluminum chloride can be prepared by slowly adding an exact amount of aluminum chloride in an inert atmosphere. The mixing ratio of aluminum chloride to EMImCl can be between 5:1 and 1:1, or about 1.5:1.

[0078]

[0082] In some embodiments, the water-in-salt electrolyte is gelled, Positive electrode solution and / or Negative electrode solution can be used as. The water-in-salt electrolyte can include an electrolyte with a salt concentration exceeding the saturation point. By increasing the salt concentration beyond the saturation point to form the water-in-salt electrolyte, the activity of water in the aqueous electrolyte can be further reduced. The ionic conductivity of such an electrolyte can be higher than that of a normal aqueous electrolyte. The water-in-salt electrolyte can include water with a suitable salt exceeding its saturation point, including any of the salts and additives described herein for aqueous Negative electrode solution and / or aqueous Positive electrode solution

[0079]

[0083] To prevent neutralization, Negative electrode solution and Positive electrode solutionIt is necessary to separate or disconnect. Such separation can be achieved by using a separator through gelation or polymerization of the electrolyte, and any combination thereof.

[0080]

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

[0081]

[0085] As described herein, the electrolyte is polymerized or gelled to Positive electrode solution and / or Negative electrode solutionA polymer gel electrolyte (PGE) for use can be formed. The resulting PGE can be in a semi-solid state that resists the 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, the method of forming the PGE can begin with the selection of monomer materials for the PGE. The monomer can be a polar vinyl monomer selected from the group consisting of acrylic acid, vinyl acetate, acrylic esters, vinyl isocyanate, acrylonitrile, or any combination thereof. Thereafter, the components of the aqueous electrolyte can be selected and the electrolyte can include any of the above components. To initiate the polymerization process, an initiator can be added. In some embodiments, a cross-linking agent can be used in the electrolyte composition to further cross-link 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 wt% and about 50 wt%, the initiator can be present in an amount between about 0.001 wt% and about 0.1 wt%, and the cross-linking agent can be present in an amount between 0 and 5 wt%.

[0082]

[0086] In some embodiments, the PGE can be formed in situ, which refers to introducing the electrolyte as a liquid into the housing and then polymerizing it to form the PGE within the housing. This method can allow the electrolyte composition to be immersed in the voids, anode, and / or cathode before fully polymerizing to form the PGE. In some embodiments, a vacuum (e.g., a pressure lower than atmospheric pressure) can be created within the housing 7 when introducing the electrolyte into the corresponding compartments. The vacuum can 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 can be between about 10 inches and 29.9 inches of mercury column, or between about 20 inches and about 29.9 inches of mercury column of vacuum. The use of the vacuum can help avoid the presence of air pockets within the battery 10 before complete polymerization of the electrolyte. In some embodiments, the electrodes can be immersed in the electrolyte solution for between 1 and 120 minutes at a temperature between 0°C and 30°C before complete polymerization of the electrolyte to allow the electrolyte to impregnate the electrodes. Once the electrolyte is polymerized, the battery can be rested before use. In some embodiments, the battery can be rested between 5 minutes and 24 hours.

[0083]

[0087] To help impregnate the electrodes with the electrolyte, the electrodes can be pre - immersed in a selected electrolyte solution before polymerizing the electrolyte. This can be to the electrolyte outside the battery or housing (e.g., Positive electrode solution or Negative electrode solutionIt can be performed by separately dipping the electrodes and then constructing a battery by placing the pre-dipped electrodes into a housing. In some embodiments, an electrolyte that does not contain a polymer or gelling agent can be introduced into the battery to dip the electrodes in situ. This can include the use of a vacuum to assist in impregnating the electrodes. The electrodes can be dipped for a period between about 1 minute and 24 hours. In some embodiments, the dipping can be performed over a plurality of cycles where the battery is filled with electrolyte, made dip-able, drained, refilled, and made dip-able again and drained the desired number of times. Once the electrodes are dipped and impregnated with the electrolyte, the electrolyte containing the polymer and polymerization agents (e.g., initiator, cross-linking agent, etc.) can be introduced into the housing and made polymerizable to form the final battery.

[0084]

[0088] The composition of the electrolyte, monomer material, initiator, and conditions of formation (e.g., temperature, etc.) can be selected to provide a desired polymerization time such that the electrolyte composition can properly dip and be absorbed and penetrate into the battery components. The temperature can be controlled to control the polymerization process, where a relatively low temperature can suppress or slow down the polymerization, and a relatively high temperature can shorten the polymerization time or accelerate the polymerization process. Also, an increase in the alkaline electrolyte component (e.g., hydroxide) can shorten the polymerization time, and an increase in the initiator concentration will shorten the polymerization time. The appropriate polymerization time can be between 1 minute and 24 hours based on the composition of the electrolyte solution and the temperature of the reaction.

[0085]

[0089] In some embodiments, Negative electrode solution and / or Positive electrode solution can be formed via a gelling process such as free radical polymerization techniques where, for example, acrylic acid can be used as the monomer. Acrylic acid can be mixed with Negative electrode solution or Positive electrode solution until it is substantially dissolved. A cross-linking agent such as N,N’-methylenebisacrylamide (MBA) can be used to increase the strength of the polymer. An acidic electrolyte (e.g., Negative electrode solutionIn the case of , the process of mixing acrylic acid and MBA can usually be carried out at a relatively low temperature due to the heat generated in the reaction. However, in the case of an alkaline electrolyte (e.g., Positive electrode solution ), the mixture of acrylic acid and MBA can be heated to 50 - 200 °C. The polymerization can be initiated through the addition of an initiator such as a salt of persulfate, such as potassium persulfate, sodium persulfate, ammonium persulfate, or any combination thereof. The electrolyte additives disclosed herein (e.g., Negative electrode solution additive, Positive electrode solution additive) can be included during the gelation process. Ionomers can also be added during the gelation process. Non-limiting examples of ionomers that can be added to the electrolyte during the gelation process include perfluorosulfonic acid (PFSA) / polytetrafluoroethylene (PTFE) copolymer in acid form, or Nafion solution made from an anion exchange ionomer having a polyaromatic polymer.

[0086]

[0090] As an example of the polymerization process, a mixture of acrylic acid, N,N’-methylenebisacrylamide, and an alkaline solution can be produced at a temperature of about 0 °C. Thereafter, any additives can be added to the solution (e.g., gas generation inhibitors, additional additives described herein, etc.). For example, when used in an electrolyte, the electrolyte additive can be dissolved in an alkaline solution after mixing the precursor components, and the electrolyte additive can be beneficial during the electrochemical cycle of the electrode. To polymerize the resulting mixture, an initiator such as potassium persulfate can be added to initiate the polymerization process and form a solid or semi-solid polymer electrolyte (e.g., PGE). The resulting polymer electrolyte can be stable over time when the polymerization process occurs.

[0087]

[0091] As an example, the PGE described herein can be made through a free radical polymerization process. In certain embodiments, acrylic acid (AA) can be used as a monomer, along with N,N’-methylenebisacrylamide (MBA) as a crosslinking agent and potassium persulfate (K2S2O8) as an initiator. Negative electrode solutionWhen preparing the solution, an alkaline electrolyte such as KOH may be added to the process. Negative electrode solution 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 electrode solution When preparing the acid electrolyte, such as sulfuric acid, may be added to the process. Positive electrode solution 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 electrode solution Gel and / or Positive electrode solution 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 the construction of the battery 10 or after the cells are constructed. In some embodiments, the electrolyte can be polymerized and placed in a tray to form a sheet. Once polymerized, the sheet can be cut to the appropriate size and shape, and one or more layers can be used to form the electrolyte that contacts the electrodes. When using pre-formed PGE, 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 can be formed using an aqueous electrolyte, an organic electrolyte, an ionic liquid, a water-in-salt electrolyte, etc. In some embodiments, the aqueous electrolyte can be Positive electrode solution and / or Negative electrode solution used and gelled to form an aqueous hydrogel as the PGE. In some embodiments, the aqueous hydrogel can be created through a free radical polymerization process. For example, Negative electrode solution when preparing, acrylic acid (AA) can be selected as the monomer, together with N,N'-methylenebisacrylamide (MBA) as the cross-linking agent and potassium persulfate as the initiator. In aqueous alkali Negative electrode solution , an appropriate hydroxide (e.g., potassium hydroxide (KOH), sodium hydroxide, lithium hydroxide, etc.) can be used to form the electrolyte. By neutralizing the hydroxide with AA, the hydroxide can be encapsulated in the hydrogel network. To create the hydrogel, the monomer can be combined with any cross-linking agent until the cross-linking agent is dissolved. Alternatively, an amount of hydroxide can be cooled to slow down the reaction. Negative electrode solutionIn some embodiments where the electrolyte is aqueous, the hydroxide can be cooled to a temperature of less than about 10 °C, less than about 5 °C, or less than about 0 °C. And since the neutralization reaction releases heat, the mixed solution of the monomer and any crosslinking agent can be dropped into the cooled solution of the hydroxide. To gel the resulting mixture of hydroxide, monomer, and crosslinking agent, an initiator such as potassium persulfate can be added. Thereafter, the mixture can enable the formation of PGE. The amounts and concentrations of the components can be varied to obtain various mechanical strengths of the hydrogel. Similarly, Positive electrode solution When preparing, an acidic electrolyte such as sulfuric acid can be encapsulated within the hydrogel network.

[0091]

[0095] An electrolyte containing an ionic liquid can also be used to form a PGE containing any of the ionic liquids described herein. To form a PGE using an ionic liquid, a solution of any additives that can be included 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 polymerizing agent for the ionic liquid. To this solution, the ionic liquid together with the additive solution can be mixed together with an initiator. Any suitable initiator for use with the polymerizing agent can be used. For example, azobisisobutyronitrile can be used together with acrylamide. The initiator can be added in a suitable amount such as about 1 wt% of the polymerizing agent. Thereafter, this final solution can be heated to form a polymerized gel.

[0092]

[0096] An organic electrolyte containing a salt dissolved in an organic solvent can also Negative electrode solution and / or Positive electrode solutionIt can be gelled to form. As an example, a lithium-ion conductive electrolyte can be gelled using several polymerization techniques such as ring-opening polymerization, photo-initiated radical polymerization, UV-initiated radical polymerization, thermal-initiated polymerization, in-situ polymerization, UV irradiation, electrospinning, etc. The lithium electrolyte can contain lithium hexafluorophosphate (LiPF6), lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(oxalato)borate, and combinations thereof in an organic solvent such as ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate, and combinations thereof. An exemplary mixture can include 1M LiPF6 mixed in a solvent mixture of ethylene carbonate and dimethyl carbonate. Other solvents that can be used as mixtures to reduce the flammability of the organic electrolyte also exist.

[0093]

[0097] The organic electrolyte can be gelled by mixing a selected salt with an organic solvent. Thereafter, a gelling agent can be added together 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 - 90 °C, or about 70 °C, and holding for 1 - 24 hours.

[0094]

[0098] Positive electrode solutionIn the case of an essentially acidic aqueous electrolyte such as, etc., polymerization can be carried out using many processes. In certain embodiments, a method of making an acidic solid-gelled aqueous electrolyte can include the addition of acrylamide to a solution containing manganese sulfate, H2SO4, ammonium sulfate, potassium permanganate, and / or sulfuric acid. A gelling agent containing acrylamide is added to the solution and can be mixed at a temperature between about 70 to 90 °C for at least 1 hour until the solution becomes homogeneous. After the solution is well mixed, a cross-linking agent and an initiator are added to the solution and can be mixed for 2 to 48 hours until the solution gels.

[0095]

[0099] In some embodiments, the separator includes an ion-selective gel, and the ion-selective gel includes 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, NaSiCON, LiSiCON, or any combination thereof.

[0096]

[0100] Negative electrode solution PGE and Positive electrode solution PGE can be used without a separator, but Positive electrode solution and Negative electrode solution the separation of can also be carried out through an ion-selective ceramic separator and / or a polymer membrane. A cellulose-based membrane such as cellophane can also Positive electrode solution and Negative electrode solution be used to separate. For example, a ceramic separator such as LiSiCON and / or NaSiCON can Positive electrode solution and Negative electrode solution be used to separate. As another example, a polymer membrane having cation exchange properties such as Nafion, and / or an anion exchange membrane can Positive electrode solution and Negative electrode solution be used to separate. Polyvinyl alcohol (PVA) and / or cross-linked polyvinyl alcohol (C-PVA) can also Positive electrode solution and Negative electrode solutionIt can be used as a polymer separator to separate. Cellulose-based membranes, PVA, and C-PVA can be grafted with ionomers that can impart cationic and / or anionic exchange properties. Bipolar membranes can also be Positive electrode solution and Negative electrode solution used as a separator between.

[0097]

[0101] Gels or polymer membranes containing LiSiCON and NaSiCON can be prepared using the procedures described herein for the formation of PGE and / or ionogel layers by using the raw materials used to create ceramic separators.

[0098]

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

[0099]

[0103] Since there are no metal electrodes in the high-voltage metal-free batteries disclosed herein, there are no problems with dendrites or short circuits in the display.

[0100]

[0104] In the final cell or battery design, an acidic PGE with a separator or buffer layer that prevents mixing of the two PGEs Positive electrode solution containing cathode and an alkaline PGE Negative electrode solution containing anode can be used. Batteries with dual electrolytes enable high reversibility of the electrodes, and improved or maximum utilization, and thus higher energy density. Negative electrode solution and Positive electrode solution The use of significantly different alkalinities and acidities in also further enables the average discharge of the battery to increase beyond 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 may 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 during discharge to form an anodic oxide material; and (ii) charging the high-voltage metal-free battery to a charge voltage, wherein at least a portion of the anodic oxide material is reduced to the anode electroactive material during charging. The discharge voltage can be greater than 1.6V, or about 2V or more, or about 3V or more, or about 3.5V or more, or from greater than 1.6V to about 5V, or from about 2V to about 5V, or from about 3V to about 5V, or from about 3.5V to about 5V.

[0102] Example

[0106] While the subject matter has been generally described, the following examples are provided as specific aspects of the disclosure and are included to demonstrate its implementation and advantages, as well as the preferred aspects and features of the invention. The techniques disclosed in the following examples represent techniques that the inventors have discovered to function well in the practice of the invention and can, therefore, be considered to constitute a preferred mode for its implementation. However, one skilled in the art should understand that, in light of this disclosure, many modifications can be made to the specific aspects disclosed and similar or like results can be obtained without departing from the scope of the invention of this disclosure. It should be understood that the examples are provided by way of illustration and are not intended to limit the specification of the claims that follow in any way.

[0103] Example 1

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

[0104]

[0108] Manganese dioxide (MnO₂), more specifically electrolytic manganese dioxide (EMD), was selected as an exemplary cathode system. The OCV of a conventional or customary alkaline MnO₂|Zn battery is about 1.6 V. In a high-voltage metal-free MnO₂|hausmannite (Mn₃O₄) aqueous battery, the OCV is defined by the Positive electrode solution and Negative electrode solution concentrations used. For the rechargeable battery, the Positive electrode solution used was 3 M sulfuric acid containing 0.5 M manganese sulfate as an additive, and the Negative electrode solution used was 25 wt% potassium hydroxide. The cathode composition was 80 wt% MnO₂, 15 wt% expanded graphite, and 5 wt% Teflon affixed on a titanium current collector, and the anode composition was similar to bismuth oxide as an additive affixed on a nickel current collector. Nafion 115 was used as the ion-selective membrane separator. The OCV of this battery was about 1.6 V. The cathode and anode were monitored against a reference electrode, and their potentials are shown in FIG. 2 together with the battery voltage. FIG. 2 shows the performance of a rechargeable electrolytic manganese dioxide (MnO₂)|hausmannite (Mn₃O₄) battery in terms of the battery voltage with respect to Mn₃O₄, the cathode (MnO₂) with respect to mercury|mercuric oxide (Hg|HgO), and the anode (Mn₃O₄) with respect to the Hg|HgO reference electrode, and the Positive electrode solution used was 3 M sulfuric acid and 0.5 M manganese sulfate, and the Negative electrode solution used was 25 wt% potassium hydroxide. MnO₂ was cyclable at capacities of 1 electron (308 mAh / g) and 2 electrons (617 mAh / g). This battery was cyclable many times at its rated capacity without loss of voltage and capacity, as shown in FIG. 2.

[0105] Example 2

[0109] Another high-voltage metal-free MnO2|Mn3O4 aqueous battery was assembled with the same cathode and anode mixing composition as described in Example 1, unless otherwise indicated herein. MnO2|Mn3O4 with the same experimental details as described in Example 1 was assembled for the primary discharge test and compared with a conventional or traditional alkaline MnO2|Zn battery. The Positive electrode solution used was 16M sulfuric acid, while the Negative electrode solution used was 45 wt% potassium hydroxide. The OCV of this battery was about 2.2V, 0.6V higher than that of a conventional alkaline battery. Regarding the discharge performance, as shown in Figure 3, the new metal-free battery was able to deliver higher energy compared to the energy delivered by a conventional alkaline battery. 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, and the electrolyte used in the new metal-free MnO2|Mn3O4 battery was Positive electrode solution 16M sulfuric acid as Negative electrode solution 45 wt% potassium hydroxide as. As shown in Figure 3, the new MnO2|Mn3O4 battery can have better performance than a 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 the same as the cathodes described in Examples 1 and 2. The anode of Example 3 was manganese oxide (MnO) having a theoretical capacity of about 750 mAh / g. This anode (MnO) had the same composition as described for the anode of Example 1, but had bismuth oxide as an electrode additive. This anode material (MnO-based anode) was attached to a nickel mesh having copper as a backing material. The discharge performance of this new battery chemistry MnO2|MnO was tested by individually measuring the voltages of each cathode and anode, and the data are shown in Figure 4. Figure 4 shows the discharge capacity of the electrolytic manganese dioxide (MnO2)|manganese oxide (MnO) battery, and the Positive electrode solution used as additives were 5M sulfuric acid and 3.2M manganese sulfate, and the Negative electrode solution was 25 wt% potassium hydroxide. The average discharge voltage of this battery was about 1.7 V, which was higher than the average discharge voltage of conventional or traditional alkaline batteries. The MnO2 cathode was tested at its theoretical second electron capacity and could be achieved. In a higher concentration of acidic electrolyte, as can be seen from the flatness of the cathode curve, the cathode appears to undergo a direct dissolution-precipitation reaction. MnO is known to undergo a direct dissolution-precipitation reaction.

[0107] Example 4

[0111] The characteristics of another high-voltage metal-free battery were investigated. The cathode used was γ-MnO2. This cathode was fabricated in situ by the conversion of electrolytic manganese dioxide. The cathode formulation was the same as the cathode described in Example 1. The anode of Example 4 was birnessite (δ-MnO2). This new system (γ-MnO2|δ-MnO2) is demonstrated for the first time in the patent or academic literature of a complete single redox-active Mn element system battery where both the cathode and anode are MnO2. δ-MnO2 can be synthesized ex situ or in situ. δ-MnO2 was fabricated in situ through a formation process starting from electrolytic manganese dioxide mixed with bismuth oxide and copper. After formation, the cathode becomes copper-intercalated bismuth birnessite. The anode used in Example 4 had the same composition as the anode described in Example 1 and was pasted onto a nickel mesh. The discharge performance of this new battery chemistry γ-MnO2|δ-MnO2 was tested by measuring the voltages of the respective cathode and anode individually. This is shown in Figure 5. Figure 5 shows the discharge capacity of the gamma-manganese dioxide (γ-MnO2)|birnessite (δ-MnO2) battery, and the Positive electrode solution was 3.5 M sulfuric acid containing 3.2 M manganese sulfate, and the Negative electrode solution was 25 wt% potassium hydroxide. The average discharge voltage of this battery was about 1.7 V, which was higher than that of conventional or traditional alkaline batteries. A sigmoid-shaped curve indicating proton insertion and a flat-shaped curve indicating dissolution-precipitation of γ-MnO2 were seen in Figure 5. The cathode was 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 the patent or academic literature.

[0108] Additional Disclosure

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

[0109]

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

[0110]

[0114] A second aspect is the battery of the first aspect, wherein the cathode electroactive material includes 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 ferrate (K2FeO4), barium ferrate (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 a combination thereof.

[0111]

[0115] The third aspect is the battery of the first aspect, wherein the anode material is 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 ferrate (K2FeO4), barium ferrate (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 a combination thereof.

[0112]

[0116] The fourth aspect is the battery of the first aspect, wherein the cathode and the anode comprise conductive carbon having cathode and anode active materials including graphite, carbon fiber, carbon black, acetylene black, single-walled carbon nanotubes, multi-walled carbon nanotubes, nickel- or copper-coated carbon nanotubes, a dispersion of single-walled carbon nanotubes, a dispersion of multi-walled carbon nanotubes, graphene, graphyne, graphene oxide, or a combination thereof.

[0113]

[0117] The fifth aspect is the battery of the first aspect, wherein the cathode and the anode comprise an additive or dopant including 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] The sixth aspect is the battery of the first aspect, wherein the cathode and the anode contain a binder including 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 (registered trademark), or a combination thereof.

[0115]

[0119] The seventh aspect is the battery of any one of the first, second, third, fourth, fifth, and sixth aspects, wherein the cathode and the anode are pressed onto a current collector including carbon, lead, nickel, steel (e.g., stainless steel, etc.), nickel-coated steel, nickel-plated copper, tin-coated steel, copper-plated nickel, silver-coated copper, copper, magnesium, aluminum, tin, iron, platinum, silver, gold, titanium, bismuth, titanium, cold-rolled steel, half nickel and half copper, carbon foam, carbon felt, polypropylene mesh, or any combination thereof.

[0116]

[0120] The eighth aspect is the battery of the seventh aspect, 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] The ninth aspect is the battery of any one of the first, second, third, fourth, fifth, and sixth aspects, wherein the cathode and the anode contain 1 to 99% by weight of an electroactive material, 1 to 99% by weight of conductive carbon, 0 to 30% by weight of an additive, and 0 to 10% by weight of a binder.

[0118]

[0122] The tenth aspect is the battery of any one of the first aspects, wherein the highly proton-active Positive electrode solution contains hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, hydroiodic acid, trifluoro acid, or a combination thereof.

[0119]

[0123] The 11th aspect is a battery according to any one of the 1st and 10th aspects, Positive electrode solution The electrolyte additive to contains 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 carbonate, potassium bicarbonate, sodium bicarbonate, or a combination thereof.

[0120]

[0124] The 12th aspect is a battery according to any one of the 1st aspect, and has high hydroxyl activity Negative electrode solution contains 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] The 13th aspect is a battery according to any one of the 1st and 12th aspects, Negative electrode solution The electrolyte additive to contains 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] The 14th aspect is a battery according to any one of the 1st, 10th, 11th, 12th, and 13th aspects, Positive electrode solution and Negative electrode solution can be gelled or polymerized.

[0123]

[0127] Aspect 15 is the battery of Aspect 1, wherein the separator comprises an ion-selective gel made of 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] Aspect 16 is the battery of either Aspect 1 or Aspect 15, wherein the separator can be a gelled layer composed of an ion-selective ionomer and a buffer such as potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, etc., and the ionomer can be a perfluorosulfonic acid (PFSA) / polytetrafluoroethylene (PTFE) copolymer in acid form, or an anion exchange ionomer having a polyaromatic polymer.

[0125]

[0129] Aspect 17 is a high-voltage metal-free battery, comprising a cathode including a cathode electroactive material containing at least one of organic compounds, oxides, hydroxides, oxyhydroxides, sulfides, and combinations thereof, an anode including an anode electroactive material containing at least one of organic compounds, oxides, hydroxides, oxyhydroxides, sulfides, and combinations thereof, and a separator that is not in contact with the anode, has a pH less than 4, and is in contact with the cathode Positive electrode solution and a separator that is not in contact with the cathode, has a pH greater than 10, and is in contact with the anode Negative electrode solution and includes the same.

[0126]

[0130] Aspect 18 is the battery of Aspect 17, Negative electrode solution and Positive electrode solution further includes a separator disposed therebetween, and the separator has ion-selective properties.

[0127]

[0131] Aspect 19 is the battery of either Aspect 17 or Aspect 18, Negative electrode solution includes a first gel electrolyte solution, Positive electrode solutionIt contains a second gel electrolyte solution.

[0128]

[0132] The 20th aspect is a battery according to any one of the 17th to 19th aspects, wherein the cathode electroactive material is 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; potassium ferrate (K2FeO4); barium ferrate (BaFeO4); cupric 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 at least one of any mixtures thereof.

[0129]

[0133] The 21st aspect is a battery according to any one of the 17th to 20th aspects, wherein the anode electroactive material is 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; potassium ferrate (K2FeO4); barium ferrate (BaFeO4); cupric 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 at least one of any mixtures thereof.

[0130]

[0134] Aspect 22 is a battery according to any one of Aspects 17 to 21, wherein the cathode, anode, or both contain conductive carbon, and the conductive carbon is mixed with the cathode electroactive material, 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, a dispersion of single-walled carbon nanotubes, a dispersion of multi-walled carbon nanotubes, graphene, graphene, graphene oxide, and combinations thereof.

[0131]

[0135] Aspect 23 is a battery according to any one of Aspects 17 to 22, wherein the cathode, anode, or both contain an additive and / or a 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 combinations thereof.

[0132]

[0136] Aspect 24 is a battery according to any one of Aspects 17 to 23, wherein the cathode, anode, or both contain 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 combinations thereof.

[0133]

[0137] Aspect 25 is a battery according to any one of Aspects 17 to 24, wherein the cathode, anode, or both contain a cathode material pressed onto a current collector, and the current collector includes 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] Aspect 26 is a battery according to Aspect 25, wherein the current collector is a foil, mesh, perforated foil, foam, felt, fiber, porous block structure, honeycomb mesh, sponge shape, or any combination thereof.

[0135]

[0139] Aspect 27 is a battery according to any one of Aspects 17 to 26, wherein the cathode contains 1 to 99 wt% of a cathode electroactive material, 1 to 99 wt% of conductive carbon, 0 to 30 wt% of an additive and / or dopant, and 0 to 10 wt% of a binder, based on the total weight of the cathode.

[0136]

[0140] Aspect 28 is a battery according to any one of Aspects 17 to 27, wherein the anode contains 1 to 99 wt% of an anode electroactive material, 1 to 99 wt% of conductive carbon, 0 to 30 wt% of an additive and / or dopant, and 0 to 10 wt% of a binder, based on the total weight of the anode.

[0137]

[0141] Aspect 29 is a battery according to any one of Aspects 17 to 28, Positive electrode solution contains an acidic electrolyte, and the acidic electrolyte includes at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, trifluoro acid, and any mixture thereof.

[0138]

[0142] Aspect 30 is a battery according to any one of Aspects 17 to 29, wherein the acidic electrolyte is present in a concentration between about 0.1 M and about 16 M. Positive electrode solution present therein.

[0139]

[0143] Aspect 31 is a battery according to any one of Aspects 17 to 30, Positive electrode solution which Positive electrode solution contains an additive, Positive electrode solution wherein the additive contains 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 carbonate, potassium bicarbonate, sodium bicarbonate, and any mixture thereof.

[0140]

[0144] Aspect 32 is a battery according to any one of Aspects 17 to 31, Negative electrode solution which contains an alkaline electrolyte, and the alkaline electrolyte contains 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] Aspect 33 is the battery of Aspect 32, wherein the alkaline electrolyte is present in an amount of 10 to 60% by weight based on the total weight. Negative electrode solution present therein. Negative electrode solution present therein.

[0142]

[0146] Aspect 34 is a battery according to any one of Aspects 17 to 33,Negative electrode solution is Negative electrode solution including additives, Negative electrode solution wherein 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] The 35th aspect is a battery according to any one of the 17th to 34th aspects, Positive electrode solution , Negative electrode solution , or both are gelled or polymerized.

[0144]

[0148] The 36th aspect is a battery according to any one of the 2nd aspects, wherein the separator includes an ion-selective gel, and the ion-selective gel includes an ionomer, a bipolar membrane, a cation exchange membrane, an anion exchange membrane, cellophane grafted with ion selectivity, polyvinyl alcohol grafted with ion selectivity, a ceramic separator, NaSiCON, LiSiCON, or any combination thereof.

[0145]

[0149] The 37th aspect is a battery according to the 2nd aspect, wherein the separator is a gelled layer composed of an ion-selective ionomer and a buffer, and the buffer includes potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, or any combination thereof; the ionomer includes a perfluorosulfonic acid (PFSA) / polytetrafluoroethylene (PTFE) copolymer in acid form, an anion exchange ionomer having a polyaromatic polymer, or a combination thereof.

[0146]

[0150] The 38th aspect is a battery according to any one of the 17th to 37th aspects, characterized by an average discharge potential of more than about 1.6V to about 5V.

[0147]

[0151] Aspect 39 is a battery according to any one of Aspects 17 to 38, characterized by an average discharge potential of about 2V or more to about 5V.

[0148]

[0152] Aspect 40 is a high-voltage metal-free battery, comprising a cathode including a cathode electroactive material containing 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 containing at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof; a separator disposed between the anode and the cathode, not in contact with the anode, having a pH less than 2 and in contact with the cathode; and a separator disposed between the anode and the cathode, not in contact with the cathode, having a pH greater than 12 and in contact with the anode, and having ion-selective properties. Positive electrode solution and a separator disposed between the anode and the cathode, not in contact with the cathode, having a pH greater than 12 and in contact with the anode, Negative electrode solution and Negative electrode solution and Positive electrode solution disposed therebetween and having ion-selective properties.

[0149]

[0153] Aspect 41 is a battery according to Aspect 40, Positive electrode solution which contains an acidic electrolyte, the acidic electrolyte containing at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, trifluoroacetic acid, and any mixture thereof, Positive electrode solution and being present therein at a concentration between about 1M and about 16M.

[0150]

[0154] Aspect 42 is a battery according to any one of Aspects 40 and 41, Negative electrode solution which contains an alkaline electrolyte, the alkaline electrolyte containing 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 electrode solution and being present therein in an amount of 20 to 60% by weight based on the total weight of Negative electrode solution the battery.

[0151]

[0155] Aspect 43 is a battery according to any of Aspects 40 to 42, characterized by an average discharge potential of about 2V to about 5V.

[0152]

[0156] Aspect 44 is a method of forming a high-voltage metal-free battery, comprising contacting a cathode with a cathode electroactive material containing at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof, and disposing a pH less than 4 Positive electrode solution and contacting an anode with an anode electroactive material containing at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and combinations thereof, and disposing a pH greater than 10 Negative electrode solution and disposing at least one of a separator or a buffer layer between a portion not in contact with the cathode Negative electrode solution and a portion not in contact with the anode Positive electrode solution . The method includes the above steps.

[0153]

[0157] Aspect 45 is the method of Aspect 44, further comprising disposing the anode, the cathode, and the separator or the buffer layer within a housing to form a high-voltage metal-free battery. Positive electrode solution , Negative electrode solution The method further includes the above step.

[0154]

[0158] Aspect 46 is the method according to any of Aspects 44 and 45, wherein the separator or the buffer layer has ion-selective properties.

[0155]

[0159] Aspect 47 is the method according to any of Aspects 44 to 46, wherein Positive electrode solution contains an acidic electrolyte, which contains at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, triflic acid, and any mixture, and has a concentration between about 1M and about 16M Positive electrode solution present therein.

[0156]

[0160] Aspect 48 is a method according to any one of Aspects 44 to 47, wherein Negative electrode solution contains an alkaline electrolyte, and the alkaline electrolyte contains 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 electrode solution is present in an amount of 20 to 60% by weight based on the total weight of Negative electrode solution in.

[0157]

[0161] Aspect 49 is a method of generating energy, wherein the high-voltage metal-free battery includes a cathode containing a cathode electroactive material including at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and a combination thereof, and an anode containing an anode electroactive material including at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and a combination thereof, at least a part of which is oxidized during discharge to form an anodic oxide material, and a, not in contact with the anode, having a pH of less than 4, in contact with the cathode Positive electrode solution and a, not in contact with the cathode, having a pH of greater than 10, in contact with the anode Negative electrode solution and discharging the high-voltage metal-free battery including the above to a discharge voltage to generate energy, and charging the high-voltage metal-free battery to a charging voltage to reduce at least a part of the anodic oxide material to the anode electroactive material during charging.

[0158]

[0162] Aspect 50 is a method according to Aspect 49, wherein the discharge voltage is about 2 V or more.

[0159]

[0163] Aspect 51 is a method according to any one of Aspects 49 and 50, wherein Positive electrode solution contains an acidic electrolyte, and the acidic electrolyte contains at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, trifluoro acid, and any mixture thereof, at a concentration between about 1 M and about 16 MPositive electrode solution exists therein.

[0160]

[0164] The 52nd aspect is any one of the methods of the 49th to 51st aspects, Negative electrode solution which contains an alkaline electrolyte, and the alkaline electrolyte contains 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 electrode solution and is present in an amount of 20 to 60% by weight based on the total weight of Negative electrode solution exists therein.

[0161]

[0165] In this specification, embodiments are described with reference to the figures. However, since the systems and methods go beyond those limited embodiments, it will be apparent to those skilled in the art that the detailed descriptions given herein with respect to those figures are for illustrative purposes. For example, of course, those skilled in the art will recognize a number of alternative and suitable approaches in light of the teachings described herein, depending on the needs of a particular application, and will implement any given detailed function described herein beyond the selection of a particular implementation in the following embodiments described and shown. That is, there are numerous modifications and variations, too many to list, but all fall within the scope of the description herein. Also, the singular form should be construed to include the plural form, and vice versa, and the masculine form should be construed to include the feminine form, and vice versa, and suitable and alternative embodiments do not necessarily mean that the two are mutually exclusive.

[0162]

[0166] It should be further understood that the specific methodologies, compounds, materials, manufacturing techniques, uses, and applications described herein may vary and the description herein is not limited thereto. It should also be understood that the terms used herein are for the purpose of describing particular embodiments only and are not intended to be limiting of the scope of the system and method. Note that, as used in this specification and the appended claims (this application or its derivative applications), the singular forms "a", "an", and "the" include plural references unless the context clearly dictates otherwise. Thus, for example, reference to "an element" includes reference to one or more elements and equivalents thereof known to those skilled in the art. All conjunctions used should be understood in the broadest possible sense. Thus, the word "or" should be understood to have the definition of "inclusive or" rather than "exclusive or" unless the context clearly dictates otherwise. It should also be understood that the structures described herein refer to functional equivalents of such structures. Language that may be construed 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 system and method, the preferred methods, techniques, devices, and materials are described. It should also be understood that the structures described herein refer to functional equivalents of such structures. The system and method are described in detail with reference to its embodiments, as shown in the accompanying drawings.

[0164]

[0168] Other variations and modifications will be apparent to those skilled in the art from the interpretation of this disclosure. Such variations and modifications may include equivalent and other features that are already known in the art and may be used in place of or in addition to the features already described herein.

[0165]

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

[0166]

[0170] Features described in the context of separate embodiments may be provided in combination in a single embodiment. Conversely, for the sake of brevity, the various features described in the context of a single embodiment may be provided separately or in any suitable sub-combination. Applicants hereby notify that new claims may be formulated for such features and / or such combinations of features during the examination of this application or any further application derived therefrom.

Claims

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

2. The battery according to 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. The battery according to claim 1, further comprising a separator disposed between the negative electrode solution and the positive electrode solution, the separator having ion-selective properties.

4. The separator comprises an ion-selective gel, and the ion-selective gel comprises 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, NaSICON, LiSICON, or any combination thereof, the battery according to claim 3.

5. The separator is a gelled layer composed of an ion-selective ionomer and a buffer, the buffer comprises potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, or any combination thereof, and the ionomer comprises a perfluorosulfonic acid (PFSA) / polytetrafluoroethylene (PTFE) copolymer in acid form, an anion exchange ionomer having a polyaromatic polymer, or a combination thereof, the battery according to claim 3.

6. The battery according to claim 1, wherein the negative electrode solution contains a first gel electrolyte solution and the positive electrode solution contains a second gel electrolyte solution.

7. The cathode electroactive material is 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 ; 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 at least one of any mixture thereof, the battery according to claim 1.

8. The anode electroactive material is 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 ); 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 at least one of any mixture thereof, the battery according to claim 1.

9. The cathode, the anode, or both contain 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, a dispersion of single-walled carbon nanotubes, a dispersion of multi-walled carbon nanotubes, graphene, graphyne, graphene oxide, and combinations thereof. The battery according to claim 1.

10. The cathode, the anode, or both contain an additive and / or a 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 combinations thereof. The battery according to claim 1.

11. The cathode, the anode, or both contain 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 combinations thereof. The battery according to claim 1.

12. The cathode, the anode, or both contain a cathode material pressed on a current collector, and the current collector includes 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. The battery according to claim 1.

13. 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. The battery according to claim 12.

14. The cathode contains, based on the total weight of the cathode, 1 to 99% by weight of a cathode electroactive material, 1 to 99% by weight of conductive carbon, 0 to 30% by weight of an additive and / or dopant, and 0 to 10% by weight of a binder, the battery according to claim 1.

15. The anode contains, based on the total weight of the anode, 1 to 99% by weight of an anode electroactive material, 1 to 99% by weight of conductive carbon, 0 to 30% by weight of an additive and / or dopant, and 0 to 10% by weight of a binder, the battery according to claim 1.

16. The acidic electrolyte contains at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, trifluoro acid, and any mixture thereof, the battery according to claim 1.

17. The positive electrode solution contains a positive electrode solution additive, and the positive electrode solution additive contains manganese sulfate, nickel sulfate, potassium permanganate, manganese chloride, manganese acetate, manganese trifluoroacetate, bismuth chloride, bismuth nitrate, manganese nitrate, nickel sulfate, nickel nitrate, zinc sulfate, zinc chloride, zinc acetate, zinc trifluoroacetate, 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 trifluoroacetate, aluminum trifluoromethanesulfonate, aluminum chloride, aluminum nitrate, potassium sulfate, sodium sulfate, ammonium sulfate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, and any mixture thereof, the battery according to claim 1.

18. The negative electrode solution contains an alkaline electrolyte, and the alkaline electrolyte contains 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, the battery according to claim 1.

19. The battery according to claim 18, wherein the alkaline electrolyte is present in the negative electrode solution in an amount of 10 to 60% by weight based on the total weight of the negative electrode solution.

20. The negative electrode liquid contains a negative electrode liquid additive, and the negative electrode liquid additive includes 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. The battery according to claim 1.

21. The battery according to claim 1, wherein the positive electrode liquid, the negative electrode liquid, or both are gelled or polymerized.

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

23. The battery according to claim 1, wherein the battery is characterized by an average discharge potential of about 2 V or more to about 5 V.

24. A cathode including a cathode electroactive material containing at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and a combination thereof; An anode including an anode electroactive material containing at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and a combination thereof; A positive electrode liquid that is not in contact with the anode and has a pH of less than 2 and is in contact with the cathode; A negative electrode liquid that is not in contact with the cathode and has a pH exceeding 12 and is in contact with the anode; A separator having ion-selective properties and disposed between the negative electrode liquid and the positive electrode liquid; A high-voltage metal-free battery comprising:

25. The positive electrode liquid contains an acidic electrolyte, and the acidic electrolyte includes at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, trifluoroacetic acid, and any mixture thereof, and is present in the positive electrode liquid at a concentration between about 1 M and about 16 M. The battery according to claim 24.

26. The negative electrode liquid contains an alkaline electrolyte, and the alkaline electrolyte includes 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. Based on the total weight of the negative electrode liquid, it is present in the negative electrode liquid in an amount of 20 to 60% by weight. The battery according to claim 24.

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

28. A method of forming a high-voltage metal-free battery, comprising: placing a positive electrode liquid having a pH of less than 4 in contact with a cathode including a cathode electroactive material containing at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and a combination thereof; placing a negative electrode liquid having a pH greater than 10 in contact with an anode including an anode electroactive material containing at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and a combination thereof; placing at least one of a separator or a buffer layer between the negative electrode liquid not in contact with the cathode and the positive electrode liquid not in contact with the anode; including the positive electrode liquid contains an acidic electrolyte, and the acidic electrolyte includes at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, trifluoro acid, and any mixture thereof. The acidic electrolyte is present in the positive electrode liquid at a concentration between about 1 M and about 16 M.

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

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

31. The negative electrode liquid contains an alkaline electrolyte, and the alkaline electrolyte includes 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 negative electrode liquid in an amount of 20 to 60% by weight based on the total weight of the negative electrode liquid. The method according to claim 28.

32. Discharging a high-voltage metal-free battery to a discharge voltage to generate energy, wherein the high-voltage metal-free battery A cathode including a cathode electroactive material containing at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and a combination thereof; An anode including an anode electroactive material containing at least one of an organic compound, an oxide, a hydroxide, an oxyhydroxide, a sulfide, and a combination thereof, and at least a part of which is oxidized during discharge to form an anodic oxide material; A positive electrode liquid that is not in contact with the anode, has a pH of less than 2, and is in contact with the cathode; A negative electrode liquid that is not in contact with the cathode, has a pH greater than 10, and is in contact with the anode; Comprising, Charging the high-voltage metal-free battery to a charging voltage and reducing at least a part of the anodic oxide material to the anode electroactive material during charging; A method for generating energy, comprising.

33. The method according to claim 32, wherein the discharge voltage is about 2 V or more.

34. The positive electrode liquid contains an acidic electrolyte, and the acidic electrolyte includes at least one of hydrogen phosphate, bicarbonate, ammonium cation, hydrogen sulfide, acetic acid, hydrogen fluoride, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, trifluoroacetic acid, and any mixture thereof, and is present in the positive electrode liquid at a concentration between about 1 M and about 16 M. The method according to claim 32.

35. The negative electrode liquid contains an alkaline electrolyte, and the alkaline electrolyte includes 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 negative electrode liquid in an amount of 20 to 60% by weight based on the total weight of the negative electrode liquid, the method according to claim 32.

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