Hydrogen-based battery

Abstract

Disclosed herein are batteries and methods of making batteries. The batteries disclosed herein generally include a positive electrode, an electrolyte capable of conducting protons and / or hydronium ions, and a negative electrode comprising a material capable of absorbing protons and / or hydronium ions, wherein (i) the positive electrode is in contact with a positive electrode species; or (ii) the electrolyte comprises a reduced positive electrode species, or (iii) the positive electrode is in contact with a positive electrode species and the electrolyte comprises a reduced positive electrode species, and wherein the positive electrode species is an oxide of one or more metals or an oxide of a halide.

Description

Technical Field

[0001] This invention relates to batteries. In particular, this invention relates to batteries having a specific combination of redox active components (i.e., redox pairs), a proton and / or hydrated hydrogen ion conducting electrolyte, and a negative electrode material capable of storing or absorbing hydrogen in the form of protons and / or hydrated hydrogen ions, as well as methods for manufacturing such batteries and using such batteries. Background Technology

[0002] With its clean and convenient characteristics, electricity has become an indispensable part of modern human life. Currently, electrical energy can be stored using batteries. For example, electrical energy can be generated (e.g., through renewable energy sources such as wind, solar, and hydropower and / or non-renewable energy sources such as oil, coal, and natural gas) and then stored using batteries, especially secondary batteries (e.g., redox flow batteries, lead-acid batteries, and lithium-ion batteries).

[0003] Fuel cells also exist, where H2 serves as an energy reservoir (i.e., fuel) and is converted into electricity when needed. Among the many types of fuel cells, the proton exchange membrane fuel cell (PEMFC) is generally considered the most promising candidate and is ready for commercialization. To catalyze the slow oxygen reduction reaction, a high-quality loading of Pt is typically required. Furthermore, highly purified compressed H2 (which is explosive) is used as fuel. Typical PEMFCs rely on noble metals (such as Pt) to catalyze the oxygen reduction reaction, and safety concerns regarding H2 exist. These characteristics present significant obstacles hindering the widespread adoption of PEMFCs.

[0004] Lead-acid batteries have been around for over 150 years and were among the first rechargeable batteries to be used on a large scale. They use lead with lead oxide as electrodes and typically use a sulfuric acid solution as the electrolyte. Lead-acid batteries offer low energy storage costs (150–600 USD / (kW·h)), good reliability, and high efficiency (70%–90%). They are one of the most mature and widely used power technologies. However, lead-acid batteries generally have short lifespans (e.g., 500–1000 cycles), low energy density (e.g., 30–50 (Wh) / kg), narrow operating temperature range, slow charging speeds, and the potential for gas release through overcharging. Lead-acid batteries also present environmental problems.

[0005] Lithium-ion batteries (LIBs) are widely used in computers, communication devices, consumer products, and even electric vehicles. However, LIB development faces bottlenecks such as safety issues, rate capability, and energy density. For example, LIBs typically contain highly flammable and toxic components (primarily in the electrolyte), and electric vehicles are currently approaching the charge / discharge limits of current non-aqueous LIB systems.

[0006] In recent years, the utilization of renewable energy sources such as photovoltaic (solar) and wind power has increased. However, wind and photovoltaic power generation are inherently unstable and discontinuous, potentially impacting regional power grids. Large-scale energy storage is widely considered to improve grid efficiency and mitigate the imbalance between electricity supply and demand. Current large-scale energy storage and conversion technologies can be broadly categorized into several types, including mechanical energy storage (e.g., flywheel energy storage, pumped hydro storage, and compressed air energy storage), direct energy storage (e.g., supercapacitors and superconducting magnetic energy storage), chemical energy storage (e.g., fuels such as hydrogen and other chemicals), and electrochemical energy storage (e.g., secondary battery systems, supercapacitors / pseudocapacitors). Battery supercapacitor hybrid devices (BSHDs) have also been developed, potentially possessing advantageous properties (e.g., high energy density, short charging time, and high power density).

[0007] Current energy storage devices suffer from various drawbacks, and alternative energy storage devices are needed that overcome at least some of the aforementioned shortcomings. Safe, efficient, and / or inexpensive large-scale energy storage technologies are also required. Providing alternative battery types, particularly those that avoid and / or minimize the formation of gaseous components, would be advantageous. Summary of the Invention

[0008] In a first aspect, the present invention provides a battery comprising:

[0009] -positive electrode,

[0010] - An electrolyte, said electrolyte being capable of conducting protons and / or hydrated hydrogen ions; and

[0011] - Negative electrode, wherein the negative electrode comprises a material capable of absorbing protons and / or hydrated hydrogen ions;

[0012] in:

[0013] (i) The positive electrode is in contact with the positive electrode material; or

[0014] (ii) The electrolyte contains a reduced positive electrode material; or

[0015] (iii) The positive electrode is in contact with a positive electrode material and the electrolyte contains a reduced positive electrode material.

[0016] And among them:

[0017] The positive electrode material is an oxide of one or more metals or an oxide of a halide.

[0018] In a second aspect, the present invention provides a method for manufacturing a battery, the method comprising contacting an electrolyte with a negative electrode and a positive electrode, wherein:

[0019] - The electrolyte is capable of conducting protons and / or hydrated hydrogen ions, and comprises (a) protons and / or hydrated hydrogen ions and (b) a reduced positive electrode material, wherein the conjugate redox pair of the reduced positive electrode material is a positive electrode material that is an oxide of one or more metals or halides; and

[0020] - The negative electrode contains a material capable of absorbing protons and / or hydrated hydrogen ions.

[0021] In a third aspect, the present invention provides a battery manufactured by the method of the second aspect.

[0022] In a fourth aspect, the present invention provides the use of the battery of the first or third aspect for energy storage.

[0023] In a fifth aspect, the present invention provides a method for decomposing water without releasing gaseous hydrogen or gaseous oxygen, the method comprising:

[0024] 1) Contacting an electrolyte containing a reduced positive electrode material capable of being oxidized to form a positive electrode material with (a) a negative electrode containing a material capable of absorbing protons and / or hydrated hydrogen ions and (b) a positive electrode, and

[0025] 2) Applying a voltage between the negative electrode and the positive electrode oxidizes the reduced positive electrode material, forming a positive electrode material and H. + The H + The formation of hydrated hydrogen ions that associate with materials capable of absorbing protons and / or hydrated hydrogen ions.

[0026] The positive electrode material is an oxide of one or more metals or an oxide of a halide.

[0027] In a sixth aspect, the present invention provides a battery comprising:

[0028] - Positive electrode, which is capable of absorbing and releasing protons and / or hydrated hydrogen ions.

[0029] - An electrolyte, said electrolyte being capable of conducting protons and / or hydrated hydrogen ions; and

[0030] - Negative electrode, wherein the negative electrode comprises MoO3, particularly MoO3 nanofibers, capable of absorbing protons and / or hydrated hydrogen ions;

[0031] During use, protons and / or hydrated hydrogen ions move between the positive and negative electrodes. Attached Figure Description

[0032] Specific embodiments of the present invention are described below by way of example only, with reference to the accompanying drawings, wherein:

[0033] Figure 1 A schematic diagram of the battery prepared in Example 1 is shown.

[0034] Figure 2 A schematic diagram illustrating the working principle of the battery prepared in Example 1 is shown.

[0035] Figure 3a The graph shows the discharge capacity (lower / left y-axis) and coulombic efficiency (upper / right y-axis) of the battery prepared in Example 1 at different capacities versus the number of cycles (x-axis).

[0036] Figure 3b The voltage (V, y-axis) of the battery prepared in Example 1 at different discharge current densities (~7.5C, ~30C, ~87.5C, ~180C, and ~900C) versus capacity per gram (mAh g) is shown. -1 The graph (x-axis) shows the C-rate calculation based on discharge time, where 1C indicates that the discharge process can be completed within 1 hour. In each case, the battery is first charged at a constant current to 1.8V or 0.17mAh.

[0037] Figure 3c The long-term cycling performance (discharge capacity (lower / left y-axis) and coulombic efficiency (upper / right y-axis) versus cycle number (x-axis)) of the battery prepared in Example 1 after 1000 cycles at a discharge rate of 10 mA (~85.7C) is shown in the figure.

[0038] Figure 4 The Ragone plot (specific power (W kg)) of the battery prepared in Example 1 is shown. -1 ,y-axis) Specific energy (Whkg) -1 The graph (x-axis) demonstrates the excellent rate capability and energy storage capacity of the battery prepared in Example 1.

[0039] Figure 5The results and physical characterization data of the MoO3 nanofibers described in Example 2 are summarized, wherein: (a) shows the XRD pattern (intensity (arbitrary units) versus 2θ) and Rietveld refinement; (b, c) show the refined crystal structure of MoO3, where the larger purple and smaller red spheres represent Mo and O atoms, respectively; (d) is a low-magnification TEM image of the MoO3 nanofibers; (e) is an HRTEM image; (f) is a SAED pattern; and (g) shows an elemental mapping image recorded on the same nanofiber, showing the distribution of Mo (lower left) and O (lower right).

[0040] Figure 6 (a, b) are SEM images of the MoO3 nanofibers prepared in Example 2 (scale bar = 5 μm in (a) and 3 μm in (b)).

[0041] Figure 7 The summary of Example 2 describes the process at ~1mg cm -2 The results of a study on hydrogen ion storage performance under area loading are shown. (a) shows the performance at 0.5 to 10 mV s. -1 CV curves at different scan rates are shown in the inset at 0.5 mV / s. -1 (a) shows the CV curve at the peak current; (b) shows the Log(I) vs. log(V) plot at the peak current; (c) shows the charge / discharge curves from 5 to 200C; and (d) shows the rate performance from 20 to 200C.

[0042] Figure 8 This is a graph showing a comparison of the rate performance of MoO3 for hydrogen ion and lithium ion storage.

[0043] Figure 9 The results of the study on the structural changes of MoO3 nanofibers and the dynamics during hydrogen ion insertion / deintercalation, as described in Example 2, are summarized. (a) Indications of different charge and discharge states are shown; (b) Ex-situ XRD patterns are shown; (c) Ex-situ Raman spectra are shown; (d) Proposed crystal structures of pristine MoO3, MoO3 discharged to -0.5V, and MoO3 charged to 0.3V are shown; and (e) Nyquist plots of MoO3 with hydrogen and lithium ion storage are shown (the inset is Z' versus ω in the low-frequency range). -1 / 2 picture).

[0044] Figure 10 The following figures are shown: (a) a thickness versus area loading plot of the MoO3 electrode from Example 2; and (b) an area capacity versus area loading plot of the electrode as described in Example 2 measured in the second cycle.

[0045] Figure 11 The results of the study on hydrogen ion storage performance under high areal loading as described in Example 2 are summarized. (a) shows the MoO3 electrode (49 mg cm⁻¹). -2 (a) is an image of the cross-sectional mapping of MoO3 (yellow signals represent Mo from MoO3 and red signals represent C from carbon fiber paper); (b) is an image showing the cross-sectional mapping of MoO3 at 18 mA cm⁻¹. -2 The graph shows the areal capacity of electrodes with different loadings at current densities. (c) shows the areal capacity at 2C (400mA g) -1 (d) shows the specific capacity of electrodes with different areal loadings; (d) shows the specific capacity of a high areal loading electrode (10 mg cm⁻¹). -2 (a) is a graph showing the rate performance from 3 to 30C; (e) is a graph showing the areal capacity of the electrodes of this work compared to various energy storage devices: lithium-sulfur batteries (Li-S), lithium-ion batteries (LIB), sodium-ion batteries (SIB), lithium-ion microcells (LIMB), and supercapacitors.

[0046] Figure 12 This is a series of SEM images showing cross-sections of the MoO3 electrode of Example 2 before cycling and after 10 cycles of hydrogen ion storage / release. Specifically, (a, b) shows 1 mg cm⁻¹ -2 (c, d) shows 10 mg cm -2 ; and (e, f) shows 20 mg cm -2 .

[0047] Figure 13 This illustrates the material of Example 2 at 2mV s -1 The graph shows the CV curves for the first three cycles at the specified scan rate.

[0048] Figure 14 This shows the results at 18 mA cm during the first 50 cycles. -2 A graph showing the areal capacity of electrodes with different loads (as described in Example 2) at different current densities.

[0049] Figure 15 This shows the electrode with different areal loadings (1.25–82.51 mg cm⁻¹) at a current density of 2C during the first 50 cycles. -2 The specific capacity graph (as described in Example 2) shows that the area loading is 1-35 mg / cm³. -2 The electrodes exhibit very similar specific capacities. When the areal loading increases to 82.51 mg / cm², -2 Even at this time, the MoO3 electrode still exhibits high activity and useful discharge capacity.

[0050] Figure 16 This shows that at a current density of 15C, 10mg cm⁻¹ -2 A graph showing the cycling performance and coulombic efficiency of the electrode (as described in Example 2). The coulombic efficiency stabilizes at ~100%, indicating the high coulombic efficiency of the high areal loading electrode.

[0051] Figure 17 This is a schematic diagram of the battery cell described in Example 3. The positive electrode process is on the left-hand side, and it shows the positive electrode material MnO2 and the reduced positive electrode material Mn. 2+ The conversion between and the movement to / from the electrolyte are shown. The negative electrode process is on the right-hand side, and the expected chemical structure of the MoO3 complex involved is illustrated.

[0052] Figure 18 The basic electrochemical properties of the battery cell described in Example 3 are shown. All data were tested in standard glassware cells (sealed beaker cell and H cell). (a) Voltage (V, y-axis) versus capacity per gram (mAhg) is shown. -1 (a) Plots of the normalized capacity for a complete charge / discharge cycle (x-axis). The inset shows the normalized capacity for a complete charge / discharge cycle; (b) shows the capacity at different charge / discharge rates (20, 15, 10, 8, 5, 3, 2, 1 A g). -1 (From left to right) Voltage (V, y-axis) versus capacity per gram (mAh g) -1 (c) shows a plot of voltage (V, y-axis) versus time (min, x-axis) over multiple charge-discharge cycles; and (d) is a plot showing cycle performance and coulombic efficiency.

[0053] Figure 19 This is an exploded view of the customized battery device as described in Example 3.

[0054] Figure 20a yes Figure 19 The image shows a photograph of the custom battery device illustrated in Example 3.

[0055] Figure 20b The example described in Embodiment 3 is shown and in Figure 20a The battery cell shown in the image operates at 40mA (corresponding to 2Ag). -1 Voltage (V, y-axis) during charging and discharging versus capacity per gram (mAh g) -1 A graph (x-axis).

[0056] Figure 20c This illustrates the description in Embodiment 3 and in Figure 20a The graph shows the cycle performance and coulombic efficiency of the battery cell. The coulombic efficiency stabilizes at approximately 97%.

[0057] Figure 20d It is shown Figure 20aThe graph shows the charge-discharge curves of the battery cell described in the paper, which represent the higher mass load performance (performed at a current of 125 mA). Detailed Implementation

[0058] The following description is merely an example of a specific embodiment of the present invention.

[0059] Battery

[0060] In a first aspect, the present invention provides a battery comprising:

[0061] -positive electrode,

[0062] - An electrolyte, said electrolyte being capable of conducting protons and / or hydrated hydrogen ions; and

[0063] - Negative electrode, wherein the negative electrode comprises a material capable of absorbing protons and / or hydrated hydrogen ions;

[0064] in:

[0065] (i) The positive electrode is in contact with the positive electrode material; or

[0066] (ii) The electrolyte contains a reduced positive electrode material; or

[0067] (iii) The positive electrode is in contact with a positive electrode material and the electrolyte contains a reduced positive electrode material.

[0068] And among them:

[0069] The positive electrode material is an oxide of one or more metals or an oxide of a halide.

[0070] As those skilled in the art will understand, when using a battery, the "positive electrode material" and the "reduced positive electrode material" serve as a redox pair on the positive electrode side. That is, the "reduced positive electrode material" and the "positive electrode material" can be described as a "conjugate redox pair." In some embodiments, the conjugate redox pair is stable and active (i.e., capable of providing capacity through electrochemical reactions).

[0071] Advantageously, the batteries of the present invention typically do not involve gaseous components (e.g., no gaseous fuels as commonly found in PEMFCs), thus eliminating the need for complex pressure-resistant devices to store gaseous components. Furthermore, the formation of the gas phase typically results in a specific volumetric variation of approximately 10. 4 The difference in voltage (under atmospheric pressure) can lead to a large overpotential and cause safety issues.

[0072] In some embodiments, the battery is a secondary battery. In some embodiments, when the secondary battery is charged, reduced positive electrode material contacts (electrically or possibly physically) the positive electrode and is oxidized to form the positive electrode material. Conversely, when the secondary battery is discharged, the positive electrode material contacts (electrically or possibly physically) the positive electrode and is reduced to form reduced positive electrode material, which can then be transferred to the electrolyte. In some embodiments, when the secondary battery is charged, reduced positive electrode material is oxidized (to form the positive electrode material) and deposited on the positive electrode as a condensed phase. Conversely, when the secondary battery is discharged, the positive electrode material contacts (electrically or possibly physically) the positive electrode and is reduced to form reduced positive electrode material, which is released from the condensed phase into the electrolyte in the form of mobile reduced positive electrode material.

[0073] In some implementations, the battery is a primary battery. When the battery is constructed as a primary battery, it is assembled to have a positive electrode material in contact with the positive electrode.

[0074] As used herein, the term "battery" is used broadly to include conventional types of batteries as well as "battery-supercapacitor-hybrid-devices" (BSCHDs). Both batteries and supercapacitors rely on electrochemical processes; however, the different electrochemical mechanisms behind each of these processes provide different charge storage properties. The distinction between batteries and supercapacitors is not always clear. A recent report attempted to characterize batteries and supercapacitors ("Where Do Batteries End and Supercapacitors Begin?" Science Magazine 2014 343(6176):1210-1211). In some embodiments, the battery of the present invention can be described as a battery-supercapacitor hybrid device. A battery-supercapacitor hybrid device comprises a battery-type electrode and a supercapacitor-type or pseudocapacitor-type electrode. Such a BSCH device can integrate the advantages of both batteries and supercapacitors with favorable electrochemical performance (e.g., high energy density from the battery side and / or high charge / discharge rate from the supercapacitor side).

[0075] Advantageously, the battery of the present invention is not limited to any particular shape factor, size, weight, or capacity. For example, the battery can be configured in sizes ranging from small (e.g., for handheld or portable devices) to large (e.g., for electric vehicles or for grid-scale storage).

[0076] In some embodiments, the battery is sized like a typical consumer battery, such as AAA, AA, C, D, PP3, 18650, coin cell, or button cell (e.g., LR44 or CR20XX series, such as CR2032). Advantageously, such batteries can be used in existing devices without requiring modification or redesign to accommodate them. Furthermore, current manufacturing processes for producing the batteries will require minimal modification to manufacture the batteries according to the invention. In some embodiments, the battery is sized to have a large capacity, for example, suitable for use in electric vehicles, residential or office-scale storage, or grid-scale storage.

[0077] In some implementations, the electrolyte is non-flammable. In some implementations, the battery contains only environmentally friendly components (i.e., components that are not generally considered harmful to the environment, such as heavy metals (e.g., lead in lead-acid batteries) or other toxic components (e.g., lithium hexafluorophosphate in LIBs)).

[0078] In some embodiments, the battery contains a single electrolyte (i.e., one type of electrolyte in contact with both the negative and positive electrodes). In other embodiments, the battery contains more than one type of electrolyte; for example, one type of electrolyte contacts the negative electrode, and another type of electrolyte contacts the positive electrode. In such embodiments, the different electrolytes can be separated by a proton and / or hydrated hydrogen ion permeable membrane (e.g., a membrane). In such systems, the battery operates as two half-cells, which can be used with high-voltage redox pairs that may be incompatible with one type of electrolyte (e.g., aqueous electrolytes that cannot function because their redox potential exceeds the oxidation potential of water). In some embodiments, the electrolyte is solid and also acts as a membrane.

[0079] In some embodiments, the battery involves a flow battery-type half-reaction on the positive electrode side, the negative electrode side, or both the positive and negative electrode sides. In some embodiments, the battery involves a conventional flow battery-type half-reaction (e.g., a liquid / solution phase before and after the reaction). In some embodiments, the battery involves a solid-state flow battery-type half-reaction, which is essentially a conversion reaction in which the reactants or products are in the solid phase. Solid-state redox flow batteries differ from liquid redox flow batteries, in which the redox pair exists in the liquid phase and the products and reactants are stored in separate containers. In solid-state redox flow batteries, the redox pair coexists in the positive electrode chamber, and the separation of the redox pair can be achieved through a phase transition from solid to solid or from solid to liquid.

[0080] positive electrode

[0081] The battery of the present invention includes a positive electrode. The positive electrode typically includes a current collector portion, which is not limited to being formed of any particular material. However, the positive electrode current collector should be conductive.

[0082] In some embodiments, the current collector has a high surface area to volume ratio (e.g., XC-72, BP2000, acetylene black) and / or a high surface area to weight ratio (e.g., activated carbon black, Ketjen black).

[0083] In some embodiments, the current collector is or comprises carbon cloth. In some embodiments, the current collector is or comprises carbon fiber paper. In some embodiments, the current collector is or comprises carbon felt. In some embodiments, the current collector is or comprises metal-organic frameworks (MOFs) and / or other nanoarrays. In some embodiments, the current collector has been modified by methods that increase its specific surface area (e.g., electrodeposition or hydrothermal methods).

[0084] Redox pairs on the positive electrode side (positive electrode material and reduced positive electrode material)

[0085] Depending on the battery's state of charge, a battery may consist of a positive electrode material, a reduced positive electrode material, or both. When the battery is in use, the positive and reduced positive electrode materials act as a redox pair.

[0086] The positive electrode material is an oxide of a metal (i.e., a metal oxide), an oxide of one or more metals (which may or may not contain other nonmetallic counterions), or an oxide of a halide. Therefore, the reduced positive electrode material is a reduced form of an oxide of a metal, a reduced form of an oxide of one or more metals, or a reduced form of an oxide of a halide. In some embodiments, the positive electrode material is an oxide of a metal or an oxide of a halide. In some embodiments, the positive electrode material is an oxide of a metal (i.e., a metal oxide). In some embodiments, the positive electrode material is a binary metal oxide. In some embodiments, the binary metal oxide comprises Fe, Cu, Ni, Cr, Mn, Pb, Bi, Cr, or V, particularly V, Mn, or Pb, more particularly Mn and V. In some embodiments, the binary metal oxide comprises Mn, Pb, Bi, Cr, or V, particularly Mn or Pb, more particularly Mn. In some embodiments, the metal oxide is a polyatomic metal oxide.

[0087] Suitable metal oxides primarily include simple or complex oxide forms of common, globally abundant metals (e.g., Mn, Pb, Bi, Cr, V, Mg, Ni, Co, Fe). Simple oxide forms include binary metal oxides (e.g., MnO2). Complex metal oxide forms include polyatomic metal oxides (e.g., H2O2). a Ni b Co c Mn d O e(where ae is a numerical variable). Metals, or metal forms (e.g., their salts, their oxides, or alloys), are readily available without the hefty costs associated with precious metals. In some implementations, this can help provide cheaper and / or larger batteries. This can be important in the case of large batteries where the price may not be prohibitively high when one or more key components are abundant on Earth. Additionally, materials abundant on Earth are generally considered environmentally friendly.

[0088] In some embodiments, the oxide is also associated with noble metal elements (such as Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, and Au, which act as the host or substitute for such oxide).

[0089] In some implementations, the metals abundant on Earth are environmentally friendly. Such implementations may be preferred in terms of providing batteries that minimize or avoid the use of environmentally harmful substances.

[0090] In some implementations, the Earth-abundant metal is an Earth-abundant metal that is able to exist in at least some transition states in a high oxidation state (e.g., +4, +5, +6, +7 or +8 oxidation state).

[0091] In some implementations, the positive electrode material is an oxide or oxyacid salt of Mn, Pb, Bi, Cr, V, Cl, Br, or I.

[0092] In some implementations, the positive electrode material is MnO2, and the reduced positive electrode material is Mn. 2+ In some implementations, the positive electrode material is MnO4. - Furthermore, the reduced positive electrode material is MnO2. In some embodiments, the positive electrode material is PbO2, and the reduced positive electrode material is Pb. 2+ (For example, substances containing Pb(II), such as PbSO4). In some embodiments, the positive electrode material is Bi2O4, and the reduced positive electrode material is BiO2. + In some implementations, the positive electrode material is Cr2O7. 2- Furthermore, the reduced positive electrode material is Cr. 3+ In some implementations, the positive electrode material is VO2. + Furthermore, the reduced positive electrode material is VO 2+ In some implementations, the positive electrode material is ClO4. - Furthermore, the reduced positive electrode material is ClO3. - In some embodiments, the positive electrode material is BrO3, and the reduced positive electrode material is Br2. In some embodiments, the positive electrode material is IO3. -Furthermore, the reduced positive electrode material is I2. In some embodiments, the positive electrode material is free ions (e.g., free Cr2O7). 2- (Ions). In some embodiments, the positive electrode material is part of a solid composite (e.g., MnO2). In some embodiments, the reduced positive electrode material is free ions (e.g., free Pb). 2+ (Ions). In some embodiments, the reduced cathode material is part of a solid complex (e.g., PbSO4). Although combinations of redox pairs can be used, it is generally preferred to use a single redox pair to avoid undesirable side reactions. In some embodiments, there is a driving force for the removal of protons and / or hydrated hydrogen ions from the cathode material (e.g., but not necessarily theoretically, the driving force for the removal of protons and / or hydrated hydrogen ions provided by the redox reaction of the metal oxide with water).

[0093] In theory, any redox pair with an electrode potential higher than that of the negative electrode counterpart (which is close to 0V relative to the SHE) can be used in the battery of the present invention. In certain embodiments, the positive redox pair provides a high electrode potential (e.g., greater than 0.9V relative to the SHE) to provide a wider range of useful voltage outputs. Therefore, the redox potential of the redox pair in the battery of the present invention is typically between about 0.9V and about 2.5V. In some embodiments, the redox pair is about 1V to about 2V, for example, about 1.1V to about 1.9V. Table 1 below shows the redox potentials of the redox pairs described in the preceding paragraph.

[0094] Table 1

[0095]

[0096] Electrolytes capable of conducting protons and / or hydrated hydrogen ions

[0097] The battery of the present invention includes components capable of conducting protons and / or hydrated hydrogen ions (H3O). +The electrolyte is an electrolyte that can be in fluid or solid form. In some embodiments, the electrolyte can be in the form of a solution, suspension, or gel. In some embodiments, the electrolyte is a solution, particularly an aqueous solution. In some embodiments, the electrolyte is a polymeric electrolyte. In some embodiments, the electrolyte is a "water-in-salt" electrolyte system. In some embodiments, the electrolyte contains more than 1% w / w H2O, for example, more than 2% w / w H2O, more than 5% w / w H2O, more than 10% w / w H2O, more than 20% w / w H2O, more than 30% w / w H2O, more than 40% w / w H2O, more than 50% w / w H2O, more than 60% w / w H2O, more than 70% w / w H2O, more than 80% w / w H2O, more than 90% w / w H2O, more than 95% w / w H2O, more than 98% w / w H2O, more than 99% w / w H2O, more than 99.5% w / w H2O, or more than 99.9% w / w H2O. In some embodiments, protons and / or hydrated hydrogen ions are present in the electrolyte in amounts of up to about 4 M (e.g., about 0.001 M to about 4 M, about 0.002 M to about 3 M, about 0.005 M to about 2 M, about 0.01 M to about 1 M, about 0.02 M to about 0.5 M, about 0.02 M to about 0.1 M, about 0.02 M to about 0.5 M, about 0.02 M to about 0.1 M, about 0.05 M to about 0.1 M, or about 0.05 M).

[0098] Hydrogen ions can be present in an aqueous electrolyte due to the presence of an acid (i.e., an electrolyte containing a certain amount of acid and a certain amount of water). Examples of acids that may be contained in an electrolyte include inorganic acids, such as H₂SO₄ and HNO₃, and organic acids, such as CH₃SO₃H and CF₃SO₃H. In some embodiments, when present, the acid is present in the electrolyte in an amount of up to about 8 M (e.g., about 0.001 M to about 4 M, about 0.002 M to about 3 M, about 0.005 M to about 2 M, about 0.01 M to about 1 M, about 0.02 M to about 0.5 M, about 0.02 M to about 0.1 M, about 0.02 M to about 0.5 M, about 0.02 M to about 0.1 M, about 0.05 M to about 0.1 M, or about 0.05 M). In some embodiments, hydrogen ions may be present due to a redox process. In some embodiments, hydrogen ions may be present due to the dissociation of water into H₂. + and OH - And then H + Hydrolysis forms H3O + However, it exists. Moderate or strong acids may be preferred, with higher concentrations being preferable.

[0099] In the discharged or partially charged state, the electrolyte contains a reduced positive electrode material. The amount of reduced positive electrode material in the electrolyte varies with the state of charge of the battery. In some embodiments, the electrolyte contains a reduced positive electrode material at a concentration ranging from substantially absent (fully charged state) to substantially saturated (discharged state). As those skilled in the art will recognize, the concentration limit in the discharge state (or pristine state) may be limited by the solubility of the reduced positive electrode material. In various embodiments, the electrolyte may contain a reduced positive electrode material at concentrations ranging from about 0.001 M to about 8 M, 0.001 M to about 7 M, about 0.001 M to about 6 M, about 0.001 M to about 5 M, about 0.001 M to about 4 M, about 0.001 M to about 3 M, about 0.001 M to about 2 M, and about 0.001 M to about 1 M. In some embodiments, the battery is assembled such that the electrolyte initially contains a reduced positive electrode material in a concentration range of about 1M to about 8M (e.g., about 2M to about 6M, about 3M to about 5M, about 3.5M to about 4.5M, or about 4M).

[0100] In some embodiments, the reduced positive electrode material is present in the electrolyte because a reduced positive electrode material is added to it. In some embodiments, the reduced positive electrode material is present in the electrolyte because of redox reactions involving the positive electrode material (i.e., redox reactions involving conjugate redox pairs).

[0101] In some implementation schemes, the reduced cathode material is Mn. 2+ Salts, such as those derived from the dissolution of MnSO4 or the reduction of MnO2. In some embodiments, the reduced cathode material is MnO2, such as those derived from MnO4. - Reduction of other intermediate substances. In some implementations, the reduced cathode material is Pb. 2+ Salts, such as those derived from the reduction of PbCl2 or PbO2. In some embodiments, the reduced cathode material is BiO2. + Salts, such as those derived from the reduction of Bi₂O₄. In some embodiments, the reduced cathode material is Cr. 3+ Salts, such as those from Cr2O7, for example 2- The reduction. In some implementations, the reducing cathode material is VO. 2+ Salt, such as, for example, from VO2 + The reduction. In some implementations, the reducing cathode material is ClO3. - Salts, such as those from ClO4 - The reduction. In some implementations, the reducing cathode material is Br2, such as, for example, derived from BrO3. -The reduction. In some implementations, the reducing cathode material is I2, such as, for example, derived from IO3. - The restoration.

[0102] The electrolyte may also contain additional components (e.g., additives) to enhance performance and / or suppress side reactions. In some embodiments, the electrolyte contains ionomers, such as Nafion ionomers. Nafion ionomers are believed to form a solid-electrolyte-interphase (SEI), particularly on electrode surfaces, especially at the negative electrode, in the form of a film. In some embodiments, when present, the additives are present in the electrolyte in an amount of up to about 50% by weight (e.g., about 0.01% to about 40% by weight, about 0.1% to about 30% by weight, about 1% to about 20% by weight, about 2% to about 10% by weight) based on the weight of the electrolyte.

[0103] Anode containing materials capable of absorbing protons and / or hydrated hydrogen ions

[0104] The battery includes a negative electrode containing a material capable of absorbing protons and / or hydrated hydrogen ions. The negative electrode containing the material capable of absorbing protons and / or hydrated hydrogen ions is typically a conductive substrate in physical contact with the material capable of absorbing protons and / or hydrated hydrogen ions. For the avoidance of doubt, absorbing protons and / or hydrated hydrogen ions includes embedding protons and / or hydrated hydrogen ions.

[0105] The conductive substrate is not limited to being formed of any particular material. The conductive substrate is preferably electrochemically inert. In some embodiments, the conductive substrate is or comprises one or more of carbon cloth, carbon fiber paper, carbon felt, titanium foil, and titanium mesh, particularly carbon fiber paper. Therefore, in some embodiments, the negative electrode comprises one or more of carbon cloth, carbon fiber paper, carbon felt (i.e., activated carbon material), titanium foil, and titanium mesh in contact with a material capable of absorbing protons and / or hydrated hydrogen ions. In some embodiments, the conductive substrate has a high surface area to volume ratio (e.g., XC-72, BP2000, acetylene black) and / or a high surface area to weight ratio (e.g., activated carbon black, Ketjen black).

[0106] Materials capable of absorbing protons and / or hydrated hydrogen ions are known. Examples include hydrated hydrogen ion intercalating materials. Examples of hydrated hydrogen ion intercalating materials (also known as hydrated hydrogen ion storage materials) include those with properties suitable for H+ ion absorption. + / H3O + Vacancies are used to form stable metallic bronze or its acidic form as stable solid transition metal oxides, such as WO3, VO2, MoO3, Nb2O5, RuO2, IrO2, Bi2O4, and their doped analogues; they have the potential to be used in H + / H3O +Vacancies are created to form stable solids or polyanionic compounds that can be converted into high-valence compounds such as VOPO4 and MoWO3PO4; effective (pseudo)capacitive materials in acidic environments, such as activated carbon with a sufficiently porous structure. In some embodiments, materials capable of absorbing protons and / or hydrated hydrogen ions are metal oxides, which can form metallic bronze (H... x MO y (or possessing certain lattice water). In some embodiments, the material capable of absorbing protons and / or hydrated hydrogen ions is a polyanionic compound that can form a stable solid (e.g., H+). x (MoWPO4) (or containing some lattice water). In some embodiments, the material capable of absorbing protons and / or hydrated hydrogen ions is a metal-organic framework Zn-PTCDA, which contains Zn as a metal core and PTCDA as an organic ligand, providing sufficient interstitial sites to store ions. In some embodiments, the material capable of absorbing protons and / or hydrated hydrogen ions is a MOF, nanoarrays, and / or one or more other nanostructures that can increase the specific surface area. In some specific embodiments, the material capable of absorbing protons and / or hydrated hydrogen ions is in the form of nanofibers. In some embodiments, the material capable of absorbing protons and / or hydrated hydrogen ions is a polycyclic aromatic solid having one or more stable carbonyl groups, such as, for example, quinones, such as anthraquinone (AQ), pyrene-4,5,9,10-tetraone (PTO), and carbonyl-containing perylene and naphthalene (e.g., N,N-dioctyl-3,4,9,10-peryl dicarboxylic dianhydride (PTCDI), peryl tetracarboxylic dianhydride (PTCDA), and 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTCDA), naphthalene tetracarboxylic dianhydride (NTCDI), terephthalic acid (PTA), and its derivatives). In some embodiments, the material capable of absorbing protons and / or hydrated hydrogen ions is selected from N,N-dioctyl-3,4,9,10-perylene dicarboxylate (PTCDI), perylene tetracarboxylic dianhydride (PTCDA), 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTCDA), naphthalene tetracarboxylic dianhydride (NTCDI), terephthalic acid (PTA), and combinations thereof. In some embodiments, the material capable of absorbing protons and / or hydrated hydrogen ions is perylene tetracarboxylic dianhydride (PTCDA).

[0107] In some specific embodiments, the material capable of absorbing protons and / or hydrated hydrogen ions is or comprises MoO3. In some embodiments, MoO3 is orthorhombic.

[0108] In some specific embodiments, the material capable of absorbing protons and / or hydrated hydrogen ions is or comprises MoO3 nanofibers. While not particularly limited by length, in some embodiments, the nanofibers have a length of about 1 μm to about 200 μm, for example, about 1 μm to about 100 μm, about 2 μm to about 50 μm, about 2 μm to about 20 μm, about 2 μm to about 10 μm, about 3 μm to about 8 μm, about 4 μm to about 6 μm, or about 5 μm. While not particularly limited by width, in some embodiments, the nanofibers have a width of about 5 nm to about 1 μm, for example, about 10 nm to about 500 nm, about 50 nm to about 400 nm, about 100 nm to about 300 nm, about 150 nm to about 250 nm, or about 200 nm.

[0109] In some embodiments, MoO3 (e.g., MoO3 nanofibers) forms a layer covering the conductive substrate. In various embodiments, and depending on the application, the thickness of this layer can be from about 0.01 mm to about 10 mm, for example, from about 0.05 mm to about 5 mm, from about 0.1 mm to about 2 mm, or from about 0.14 mm to about 1.52 mm. Advantageously, and as shown in Example 2, protons are able to penetrate the thicker layer of MoO3 nanofibers without the significant obstruction observed in some prior art electrode materials.

[0110] In some embodiments, MoO3 (e.g., MoO3 nanofibers) exhibits high specific capacity. For example, in some embodiments, MoO3 (e.g., MoO3 nanofibers) exhibits a specific capacity of about 100 to about 250 mAh g⁻¹ at 5C. -1 (For example, approximately 200 to approximately 250 mAh g) -1 The specific capacity of MoO3 (e.g., MoO3 nanofibers) is high. In some embodiments, MoO3 (e.g., MoO3 nanofibers) exhibits high rate performance. For example, in some embodiments, MoO3 (e.g., MoO3 nanofibers) exhibits charge and / or discharge rates of about 5C to about 300C (e.g., about 10C to about 250C, about 50C to about 250C, about 100C to about 250C, about 150C to about 250C, about 200C to about 250C, or about 235C). Advantageously, in some embodiments, the battery exhibits high cycle characteristics even at higher discharge rates.

[0111] In some embodiments, the areal loading of MoO3 (e.g., MoO3 nanofibers) is from about 0.01 to about 150 mg / cm³. -2 For example, approximately 1 to approximately 100 mg cm -2 Approximately 5 to approximately 100 mg cm -2 Approximately 10 to approximately 100 mg cm -2 Approximately 50 to approximately 100 mg / cm-2 Approximately 80 to approximately 100 mg cm -2 Approximately 90 to approximately 95 mg cm -2 Advantageously, and as shown in Example 2, higher areal loadings can be prepared and exhibit higher areal capacity (e.g., 90.48 mg cm³ in Example 2). -2 Electrode at 18 mAcm -2 It exhibits a capacity of 14.9 mAh cm⁻¹ at high current densities. -2 (High areal capacity). In some implementations, the areal capacity is approximately 1 to approximately 40 mAh cm⁻¹. -2 For example, approximately 2 to approximately 30 mAh cm -2 Approximately 3 to approximately 25 mAh cm -2 Approximately 10 to approximately 25 mAh cm -2 Approximately 15 to approximately 25 mAh cm -2 Or approximately 20 to approximately 25 mAh cm -2 It will be recognized that higher area capacity is advantageous for higher charging and discharging currents in batteries.

[0112] In some embodiments, materials capable of absorbing protons and / or hydrated hydrogen ions exhibit high cycling characteristics, particularly when the material is or contains MoO3 (e.g., MoO3 nanofibers). For example, in some embodiments, the material can withstand more than 100 charge / discharge cycles (e.g., >1000, >2000, >5000 cycles) without exhibiting significant capacity degradation. For example, in some embodiments, the material can withstand about 100 to about 10,000 charge / discharge cycles while retaining more than 80% (e.g., >90%, >95%, >98%, >99%, >99.5%, or >99.9%) of its initial capacity. In some embodiments, the initial capacity is taken as the capacity after about 1-5 (e.g., 3-5) cycles after the electrode material has stabilized. It will be appreciated that in some embodiments, the capacity decreases in the first few cycles but tends to stabilize to a more consistent capacity after the first few cycles.

[0113] In some embodiments, there is a driving force that enables a material capable of absorbing protons and / or hydrated hydrogen ions to accept or absorb protons and / or hydrated hydrogen ions from an electrolyte containing protons and / or hydrated hydrogen ions.

[0114] In some embodiments, the material capable of absorbing protons and / or hydrated hydrogen ions may contain other components. For example, in some embodiments, the hydrated hydrogen ion storage negative electrode material may contain a binder (e.g., Nafion, for example in an amount of up to 10, 20, or 30% by weight), a conductive agent (e.g., acetylene black, Super-P, XC-72), and / or a solvent (e.g., 2-propanol from the manufacturing process, for example in trace amounts).

[0115] Other components

[0116] In some embodiments, the battery of the present invention may include other components.

[0117] In some embodiments, the battery includes a separator. For example, a separator may be necessary when the battery is a compact battery or when the battery includes more than one type of electrolyte (e.g., a dual-electrolyte system). The separator should be proton and / or hydrated hydrogen ion permeable. In some embodiments, the battery includes a separator selected from Nafion polymer membranes, glass fiber membranes, organic porous membranes, inorganic porous membranes, filter paper, and celgard membranes.

[0118] In some implementations, the battery includes a “substrate-free” negative electrode, in which the negative electrode fluid is processed directly onto one side of the separator, or the negative electrode is processed as a separate electrode, for example, using a PTFE solution as a binder.

[0119] In some implementations, the negative and / or positive electrodes contain conductive carbon-based materials (e.g., acetylene black, XC-72, SuperP.) as conductive additives.

[0120] Charging status

[0121] As those skilled in the art will recognize, the battery of the present invention can exist in a charged state, a partially charged state, or a discharged state. When the battery is in a charged state, a large portion of the redox pairs will exist as positive electrode material (typically in contact with the positive electrode), and only a small portion will exist as reduced positive electrode material (dissolved or dispersed in the electrolyte). When the battery is in a discharged state, a large portion of the redox pairs will exist as reduced positive electrode material (dissolved or dispersed in the electrolyte), and only a small portion will exist as positive electrode material (typically in contact with the positive electrode). When the battery is in a partially charged state, the ratio of redox pairs will fall somewhere between these extremes. Therefore, in the battery of the present invention:

[0122] (i) The positive electrode is in contact with the positive electrode material; or

[0123] (ii) The electrolyte contains a reduced positive electrode material; or

[0124] (iii) The positive electrode is in contact with the positive electrode material and the electrolyte contains the reduced positive electrode material.

[0125] In this document, the term "in contact with" refers to electrical contact between the positive electrode and the positive electrode material (i.e., the ability of charge to flow from one to the other). This is typically achieved by physically contacting the positive electrode with the positive electrode material for at least a period of time. The positive electrode material is preferably a solid (i.e., in a condensed phase). When the positive electrode material is solid, it can maintain physical (and electrical) contact with the positive electrode. In some embodiments, physical contact can be generated by the positive electrode material in the form of a film on the positive electrode. In some embodiments, physical contact can be generated by the positive electrode material in the form of a coating on the positive electrode. In some embodiments, physical contact can be generated by the deposition of the positive electrode material on the positive electrode. In some embodiments, the positive electrode material is physically dispersed in the electrolyte. In such embodiments, this can create a concentration gradient during electrochemical processes, which causes concentration polarization.

[0126] Methods of manufacturing batteries

[0127] In a second aspect, the present invention provides a method for manufacturing a battery, the method comprising contacting an electrolyte with a negative electrode and a positive electrode, wherein:

[0128] - The electrolyte is capable of conducting protons and / or hydrated hydrogen ions, and comprises (a) protons and / or hydrated hydrogen ions and (b) a reduced positive electrode material, wherein the conjugate redox pair of the reduced positive electrode material is a positive electrode material that is an oxide of one or more metals or halides; and

[0129] - The negative electrode contains a material capable of absorbing protons and / or hydrated hydrogen ions.

[0130] The present invention also provides a method for manufacturing a battery, the method comprising contacting an electrolyte with a negative electrode and a positive electrode, wherein:

[0131] - The electrolyte is capable of conducting protons and / or hydrated hydrogen ions, and contains protons and / or hydrated hydrogen ions;

[0132] - The positive electrode is in contact with a positive electrode material, which is an oxide of one or more metals or an oxide of a halide; and

[0133] - The negative electrode contains a material capable of absorbing protons and / or hydrated hydrogen ions.

[0134] These methods involve contacting the electrolyte with both the negative and positive electrodes. This can be achieved in any manner, as long as the electrolyte is in contact with both the negative and positive electrodes. For example, the negative and positive electrodes can be positioned adjacent to each other, and the electrolyte is added in fluid form to contact both the negative and positive electrodes. In another arrangement, the electrolyte can be immersed in a material (e.g., a membrane, such as a glass fiber material) and sandwiched between the negative and positive electrodes, thereby contacting both. In some embodiments, the electrolyte contacting the negative electrode is the same as the electrolyte contacting the positive electrode (i.e., only one electrolyte). In other embodiments, one electrolyte contacts the negative electrode, and another electrolyte contacts the positive electrode, the two electrolytes being separated by a membrane permeable to protons and / or hydrated hydrogen ions.

[0135] Electrolytes may contain hydrated hydrogen ions. Hydrated hydrogen ions can dissociate from H₂O (e.g., from aqueous electrolytes) into H₂O. + and OH - Hydrogen ions can also be generated by the dissociation of acids (e.g., acids from an aqueous electrolyte) in the presence of water. In some embodiments, hydrogen ions are generated by a redox reaction of a redox pair. In some embodiments, hydrogen ions are generated by the addition of an acid to the electrolyte. In some embodiments, the acid is an inorganic acid, such as H₂SO₄ and HNO₃, and / or an organic acid, such as CH₃SO₃H and CF₃SO₃H. In some embodiments, the concentration of the acid in the electrolyte is from about 0.005 M to about 1 M, for example, from about 0.01 M to about 0.5 M, from about 0.01 M to about 0.1 M, or about 0.05 M. The electrolyte may contain protons. Protons can be dissociated from H₂O (e.g., from an aqueous electrolyte) into H₂O. + and OH - Protons can also be generated by the dissociation of a protic acid (e.g., an acid from an aqueous electrolyte). In some embodiments, protons are generated by a redox reaction of a redox pair. In some embodiments, protons originate from the dissociation of a protic acid.

[0136] In some embodiments, the aqueous electrolyte contains a reduced positive electrode material when the battery is manufactured. In some embodiments, the reduced positive electrode material is present in the electrolyte at an initial concentration of about 0.1 M to about 10 M, for example, about 0.5 M to about 9 M, about 1 M to about 8 M, about 2 M to about 6 M, about 3 M to about 5 M, or about 4 M.

[0137] In some embodiments, the aqueous electrolyte initially contains about 3 M to about 5 M (e.g., about 4 M) of MnSO4. In some embodiments, the aqueous electrolyte initially contains about 0.01 M to about 0.1 M (e.g., about 0.05 M) of H2SO4.

[0138] In some embodiments, the method of manufacturing the battery further includes the step of forming a positive electrode material from a reduced positive electrode material. This can be achieved by applying a voltage between the negative and positive electrodes to promote a redox reaction, which oxidizes the reduced positive electrode material (present in the electrolyte) at the positive electrode to form the positive electrode material. In some embodiments, forming the positive electrode material includes depositing the positive electrode material on the positive electrode, typically on a positive electrode current collector. In other embodiments, the positive electrode material is formed and dispersed in the electrolyte.

[0139] In some embodiments, the method further includes the step of associating / absorbing protons and / or hydrated hydrogen ions with a material capable of absorbing protons and / or hydrated hydrogen ions. This can be achieved by applying a voltage between the negative and positive electrodes to promote a redox reaction in which a reduced cathode material (present in the electrolyte) is oxidized at the positive electrode to form protons and / or hydrated hydrogen ions, which are then conducted (transported) to the negative electrode, where they associate with a material capable of absorbing protons and / or hydrated hydrogen ions. The association of protons and / or hydrated hydrogen ions with a material capable of absorbing protons and / or hydrated hydrogen ions can be described as intercalation or absorption. In the case of hydrated hydrogen ions, this can also be referred to as hydroniation. This absorption / association can also be described as a reversible capture and / or storage of protons and / or hydrated hydrogen ions.

[0140] In some embodiments, the negative electrode, comprising a material capable of absorbing protons and / or hydrated hydrogen ions, is or comprises a conductive substrate in contact with the material capable of absorbing protons and / or hydrated hydrogen ions. The material can be brought into contact with the substrate by any means that results in contact between the material and the substrate. In some embodiments, a fluid containing the material is airbrushed onto the substrate.

[0141] In some embodiments, the fluid containing the material comprises a material capable of absorbing protons and / or hydrated hydrogen ions, a binder, and a solvent. In some embodiments, the binder is a polymeric electrolyte. The polymeric electrolyte may have H... + and / or H3O + Storage sites are used to improve capacity. Polymer electrolytes are generally considered to be electronically insulating and ionicly conductive, and therefore they can be used as artificial solid-electrolyte interfaces to prevent water reduction side reactions. In some embodiments, the binder is a polymer electrolyte selected from the group consisting of: polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), Nafion, and sulfonated polyether ether ketone (SPEEK), particularly Nafion. In some embodiments, the binder is selected from carboxymethyl cellulose and xanthan gum. In some embodiments, the binder is part of the electrolyte in the assembled battery. In some embodiments, the solvent is C1-3 Alcohols, especially 2-propanol.

[0142] In some embodiments, the fluid containing the embedded material also contains a conductive additive. In some embodiments, the additive is acetylene black or XC-72R, particularly acetylene black with a large specific area.

[0143] In some implementations, the fluid containing materials capable of absorbing protons and / or hydrated hydrogen ions is in slurry form.

[0144] In some embodiments, a material capable of absorbing protons and / or hydrated hydrogen ions is contacted with a substrate by one or more of the following methods: spraying, electrospraying, roll-to-roll coating, slot-die coating (or slit extrusion coating), ultrasonic brushing, and doctor blade coating. Such methods allow the material to be uniformly coated onto the substrate. In some embodiments, the substrate is heated (e.g., about 50°C to about 150°C, about 80°C to about 120°C, about 90°C to about 110°C, or about 100°C) during or after the application of the slurry to the substrate to at least partially remove one or more components of the slurry (e.g., solvents).

[0145] The mass loading of the active material (i.e., the material capable of absorbing protons and / or hydrated hydrogen ions) can be adjusted over a wide range, for example, approximately 0.01 mg cm⁻¹. -2 Approximately 100 mg cm -2 Approximately 0.1 mg cm -2 Approximately 10 mg cm -2 Approximately 0.1 mg cm -2 Approximately 5mg cm -2 Approximately 0.5 mg cm -2 Approximately 5mg cm -2 Approximately 0.5 mg cm -2 Approximately 1 mg cm -2 Approximately 0.5 mg cm -2 Approximately 0.9 mg / cm -2 or approximately 0.7 mg cm -2 Those skilled in the art will be able to determine the appropriate amount, taking into account the effectiveness / efficiency of a particular material.

[0146] In a third aspect, the present invention provides a battery manufactured by the method of the second aspect.

[0147] Uses of batteries

[0148] Batteries, whether first or third aspect, are not limited to any particular shape factor, size, weight, or capacity. Therefore, batteries can be manufactured with a variety of shape factors, sizes, weights, or capacities that can be used in many different applications. For example, the size of the battery can be shaped like a common consumer battery, such as AAA, AA, C, D, PP3, 18650, coin cell, or button cell. Alternatively, the size of the battery can be shaped to provide a larger capacity, for example, for use in electric vehicles or grid-scale storage setups.

[0149] Therefore, in a fourth aspect, the present invention provides the use of the battery of the first or third aspect for energy storage. In some embodiments, the energy storage is the storage of renewable energy. In some embodiments, the energy storage is grid-scale energy storage. In some embodiments, the energy storage is grid-scale storage of renewable energy. In some embodiments, the energy storage is energy storage for mobile devices. In some embodiments, the energy storage is energy storage for vehicles.

[0150] Advantageously, in at least some embodiments of the invention, the transfer of protons and / or hydrated hydrogen ions in the electrolyte is rapid or even ultra-rapid, thereby providing rapid charging and / or rapid discharging (i.e., high C-value). This feature can help provide rapid response when used for grid-scale storage of renewable energy. This feature can also be used in electric vehicles or appliances (e.g., drones, tools, vehicles such as automobiles) that require high current capacity (e.g., providing sufficient current for more powerful electric motors and / or faster charging).

[0151] In a fifth aspect, the present invention provides a method for decomposing water without releasing gaseous hydrogen or gaseous oxygen, the method comprising:

[0152] 1) Contacting an electrolyte containing a reduced positive electrode material capable of being oxidized to form a positive electrode material with (a) a negative electrode containing a material capable of absorbing protons and / or hydrated hydrogen ions and (b) a positive electrode, and

[0153] 2) Applying a voltage between the negative electrode and the positive electrode oxidizes the reduced positive electrode material, forming a positive electrode material and H. + The H + The formation of hydrated hydrogen ions that associate with materials capable of absorbing protons and / or hydrated hydrogen ions.

[0154] The positive electrode material is an oxide of one or more metals or an oxide of a halide.

[0155] Advantageously, the fifth aspect of the method avoids the use of expensive catalysts, such as Pt or IrO2, typically used for water splitting in PEMFCs. In some embodiments, oxidation to form the positive electrode material includes storing oxygen from water in the positive electrode material (e.g., by introducing oxygen from water into an oxygen-containing positive electrode material).

[0156] In one embodiment, the method of splitting water is performed in reverse to provide water and electricity. In such an embodiment, the method includes:

[0157] 1) Contact the electrolyte with (a) a negative electrode and (b) a positive electrode, the negative electrode containing protons and / or hydrated hydrogen ions associated with a material capable of absorbing protons and / or hydrated hydrogen ions, and the positive electrode contacting a positive electrode material that is an oxide or halide of one or more metals, and

[0158] 2) Connect an external circuit to the negative and positive electrodes to allow charge to flow between the negative and positive electrodes (i.e., current), and thereby (a) release protons and / or hydrated hydrogen ions from the material capable of absorbing protons and / or hydrated hydrogen ions into the electrolyte, and (b) reduce the positive electrode material to form a reduced positive electrode material and H2O, which are released into the electrolyte.

[0159] In a sixth aspect, the present invention provides a battery comprising:

[0160] - A positive electrode capable of absorbing and releasing protons and / or hydrated hydrogen ions (e.g., through chemical or physical means),

[0161] - Electrolytes capable of conducting protons and / or hydrated hydrogen ions, especially aqueous electrolytes; and

[0162] - Anodes containing MoO3, particularly MoO3 nanofibers, capable of absorbing protons and / or hydrated hydrogen ions;

[0163] In this process, protons and / or hydrated hydrogen ions move between the positive and negative electrodes. In some embodiments, protons and / or hydrated hydrogen ions move between the positive and negative electrodes in a process similar to a "Newton's pendulum" (i.e., one proton and / or hydrated hydrogen ion enters the electrolyte, and different protons and / or hydrated hydrogen ions leave the electrolyte).

[0164] In some specific implementations, the positive electrode absorbs and releases protons and / or hydrated hydrogen ions through electrochemical or redox reactions.

[0165] Example

[0166] Example 1

[0167] A battery was fabricated using the shape factor of a CR2032 coin cell, and its electrochemical performance was evaluated.

[0168] Perylene tetracarboxylic dianhydride (PTCDA) (70 wt%), acetylene black (20 wt%), and Nafion ionomer (10 wt%) were combined with 2-propanol (as solvent, solvent to solid mass ratio 25:1). The mixture was stirred in a flask and sonicated using a tip sonicator to form a homogeneous electrode slurry. The slurry was then sprayed onto carbon fiber paper (an electrochemically inactive substrate with high conductivity) using an air-pumped spray gun. During spraying, the substrate was fixed to a steel plate heated to 100°C via a hot plate to evaporate the solvent. Using this method, the mass loading of the active material (PTCDA in this case) can be adjusted over a wide range. In this example, it was set to 0.7 mg cm⁻¹. -2 Then, both negative electrodes are stamped into discs for further manufacturing. Similarly, the positive electrode is stamped from carbon fiber paper.

[0169] An aqueous solution containing saturated MnSO4 (approximately 4 M) and H2SO4 (0.05 M) was used as the electrolyte, and a glass fiber membrane was used as the diaphragm.

[0170] At ambient temperature, it is approximately 50 kg / cm². 2 Under applied pressure, a coin cell is assembled using a crimping machine (approximately 0.2 mL of electrolyte and a glass fiber membrane are sandwiched between the electrodes and the positive electrode, such as...). Figure 1 (As shown). Constant current charge-discharge tests were performed at different constant current densities using the Land battery testing system. The results are shown in... Figure 3a , 3b In 3c and 4, the battery exhibits excellent electrochemical properties (quite good capacity, cycle performance, and significant rate performance) compared to current existing batteries. Notably, the Ragone plot shows that the device can combine the advantages of both batteries (high energy density) and supercapacitors (high rate performance), attributed to the ultrafast transport properties of protons / hydrated hydrogen ions. Figures 3a-3c The figure in the image is based on a diameter of ~1.007 cm. 2 The battery has an electrode area of ​​~0.7 mg and an active material (i.e., PTCDA).

[0171] Example 2

[0172] The negative electrode containing MoO3 nanofibers was studied.

[0173] Synthesis of MoO3 nanofibers

[0174] MoO3 nanofibers were synthesized via a hydrothermal method established [Sun, Z. et al. Electrochim. Acta 239, 16–24 (2017)]. In a typical experiment, (NH4)6Mo7O was stirred to synthesize the nanofibers.24 1 g of 4H₂O was dissolved in 30 mL of water. 5 mL of 70% nitric acid was added dropwise to the solution, and the mixture was stirred for 40 minutes. The mixture was then transferred to a 50 mL autoclave lined with Teflon, and the reaction was heated at 180 °C for 24 hours. The prepared MoO₃ nanofibers were filtered, washed several times with deionized water and ethanol, and then dried overnight in an oven at 70 °C.

[0175] Characterization

[0176] The crystal structure of the obtained samples was evaluated by X-ray diffraction (XRD, PANalytical, Cu Kα radiation, 45 kV, 40 mA). Morphology and microstructure were analyzed by scanning electron microscopy (SEM, QUANTA 450) and transmission electron microscopy (TEM, JEOL F200). Surface composition was analyzed by X-ray photoelectron spectroscopy (XPS, Thermo ESCALAB 250i.). Raman spectra were obtained using 514 nm excitation on a Renishaw INVIA microscope.

[0177] Electrochemical Measurement

[0178] To prepare the working electrode, 70 wt% MoO3 nanofibers, 20 wt% carbon black, and 10 wt% PVDF were dispersed in N-methylpyrrolidone and then milled for 30 minutes to form a homogeneous slurry. The slurry was spread on carbon fiber paper with dimensions of 1 cm × 2 cm and then dried overnight at 70 °C. To prepare an electrode with a high areal loading (>10 mg / cm²), the following method was employed. -2 The slurry was coated onto both sides of carbon fiber paper. Electrochemical performance was tested in a three-electrode cell comprising a MoO3 working electrode, a bulk graphite counter electrode, and a saturated calomel electrode (SCE) reference electrode. The electrolyte was either 6 M H₂SO₄ or 0.5 M Li₂SO₄ aqueous solution. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were performed using an electrochemical workstation (Autolab PGSTAT302N). Galvanostatic charge / discharge (GCD) was recorded on a multichannel battery testing system (LAND CT2001 A).

[0179] discuss

[0180] Figure 5 The XRD pattern in Figure a indicates that the synthesized sample is orthorhombic MoO3, which is confirmed by XPS results (not shown). The space group of MoO3 is Pnma, and the lattice parameter is [missing information]. and Figure 5b shows the refined crystal structure. In MoO3, bilayer MoO6 octahedrons are repeatedly arranged in the bc plane and stacked along the a-axis through van der Waals interactions. Therefore, MoO3 has a layered structure and two possible hydrogen ion insertion sites: interlayer sites (green plane) and intralayer sites (orange plane). Low-magnification TEM ( Figure 5 d) and SEM ( Figure 6 The nanofibers exhibited a uniform morphology, with a width of ~200 nm and a length of ~5 μm. To analyze the microstructure of the MoO3 nanofibers, high-resolution TEM (HRTEM), selected-area electron diffraction (SAED), and elemental mapping were recorded on the same nanofiber. The lattice fringe spacings of 0.37 nm and 0.39 nm correspond to the (010) and (001) planes of orthorhombic MoO3, respectively. Figure 5 d). The single-crystal SAED pattern is attributed to diffraction along the

[100] region axis ( Figure 5 e). HRTEM and SAED further revealed that well-crystallized MoO3 nanofibers grow along the

[010] direction, as... Figure 5 As shown in g. Furthermore, elemental mapping demonstrates the uniform distribution of Mo and O within the nanofibers.

[0181] To investigate the hydrogen storage properties of MoO3 nanofibers, the areal loading of the active material was initially kept relatively low (~1 mg cm⁻¹). -2 ). Figure 7 The illustration in figure a shows a scan rate of 0.5 mV s within a potential window of –0.5 to 0.3 V. -1 The cyclic voltammogram (CV) curve at H2O shows three pairs of redox peaks at –0.37 / –0.34V (C1 / A1), -0.02 / 0.07V (C2 / A2), and 0.02 / 0.10V (C3 / A3), indicating that H2O... + The three-step redox reaction during the insertion / extraction process exhibits a small polarization of approximately 90 mV, implying rapid reaction kinetics of the MoO3 nanofiber electrode. Figure 7 a describes the range from 0.5 to 10 mV s -1 CV studies collected at the scan rate can provide information about H + Store the dynamic information. The peak current (i) and scan rate (v) conform to the power law equation (1).

[0182] i=av b (1)

[0183] Where a and b are variable values. A b value of 0.5 is generally considered to represent an ion diffusion-controlled electrochemical process, while an a value of 1.0 represents capacitive behavior. Figure 7In b, the slopes of the log(i) versus log(v) plots for A1 / C1 and A2 / C2, i.e., the b values, are 0.53 / 0.52 and 0.55 / 0.54, respectively, indicating that the H of the MoO3 electrode... + Diffusion kinetics.

[0184] Figure 7 c shows the range from 5C to 200C (1C = 200mA g). -1 Charge / discharge curves at various rates were displayed. Even at ultra-high rates of 200C, three pairs of charge / discharge plateaus were easily distinguishable, showing excellent agreement with the CV curve. A 235mAh g / L charge was achieved at a current density of 5C. -1 The high capacity is higher than previously reported values ​​(150mAh g). -1 This is presumably because the electrolyte in this embodiment has a large number of hydrogen ions available for migration in and out of the MoO3 electrode, thus contributing to increased capacity. Notably, when the discharge process was completed rapidly within only 12 seconds, the MoO3 electrode maintained a capacity of 174 mAh g⁻¹ as the current density increased to 200C. -1 Significantly better capacity (74% at 5C). This performance is much better than that of aqueous lithium-ion batteries (which retain 15% capacity at 150C). Figure 8 This is attributed to the faster diffusion kinetics of hydrogen ions compared to lithium ions. Furthermore, as the current density returned from 200C to 20C, the average capacity recovered to 96% of the average capacity at the initial 20C (231 mAh g⁻¹). -1 , Figure 7 d) exhibits excellent rate performance.

[0185] The hydrogen content of the MoO3 electrode during the cycle was calculated according to Faraday's law. Figure 9 a) When the battery is first discharged to -0.5V, a high concentration (2.0 molar equivalent) of hydrogen ions are inserted into the MoO3 electrode to form H2O. 2.0 MoO3. During subsequent electrochemical cycles, 1.1 molar equivalents of hydrogen ions reversibly deintercalate / reintercalate into the electrode, resulting in H... 0.9 MoO3 and H 2.0 The conversion between MoO3. These changes in H content are accompanied by color changes, with only electrode IV exhibiting a deep blue color (low H content, high H). 0.9 MoO3), while others show a deep red color (high H content). The overall electrochemical reactions during charging and discharging can be described as follows.

[0186] MoO3+2.0H + +2.0e - →H 2.0 MoO3 (2)

[0187]

[0188] In-situ XRD patterns were collected under different charge / discharge states to investigate the structural evolution of the MoO3 electrode. Figure 9 b). For the pristine state, the peak at 26.6° corresponds to carbon black, while other peaks are attributed to orthorhombic MoO3 (pattern I). After the first discharge, patterns II and III in the first charge curve match well with patterns VI and V in the second discharge state, respectively, indicating highly reversible hydrogen ion insertion / deintercalation. The diffraction peaks in pattern IV (fully charged to 0.3V) are significantly different from those in pattern I, indicating that the first discharge is irreversible. This irreversible first discharge corresponds to Faraday's calculations, with 2.0 molar equivalents of hydrogen inserted into MoO3, which further explains the larger positive peak current observed in the first cycle of the CV curve ( Figure 13 ) and higher first-cycle discharge capacity ( Figure 7 d). Surprisingly, during the charging process (hydrogen ion extraction), the d-spacing of the MoO3(200) planes increased from 0.693 nm to 0.727 nm, as shown by the shift of the peak at 12.77° in spectrum II to 12.17° in spectrum IV, while decreasing during the discharging process (hydrogen ion insertion). This phenomenon is attributed to the strong electrostatic interaction between the MoO6 octahedral layer and the inserted hydrogen ions.

[0189] In-situ Raman spectroscopy ( Figure 9 c) Used to further reveal the role of H + The crystal phase change of MoO3 caused by insertion / extraction. The reversibility of Raman spectroscopy under different charge / discharge states corresponds to in-situ XRD. 600–1000 cm⁻¹ -1 The vibrational modes within this range are characteristic of orthorhombic MoO3 (e.g. Figure 9 (Highlighted in c). In its original state (spectral I), 663 cm⁻¹ -1 (B 2g B 3g ), 818cm -1 (A g B 1g ) and 991cm -1 (A g B 1g The peaks at 818 cm⁻¹ are attributed to the stretching of triple-bridged oxygen (Mo₃–O), double-bridged oxygen (Mo₂–O), and terminal oxygen atoms (Mo=O) along the c-axis. Following the first discharge process (spectrum II), the insertion of numerous hydrogen ions leads to the breaking of the Mo₂–O and Mo=O bonds, as seen at 818 cm⁻¹. -1 and 991cm -1The peaks at the specified location disappeared. Conversely, all peaks returned to their original state after charging (spectral IV), and the three types of oxygen atoms reappeared. Based on these results, the hypothetical structural evolution of MoO3 during charging and discharging is as follows: Figure 9 d is shown schematically.

[0190] The hydrogen ion diffusion kinetics of the MoO3 electrode were further evaluated using electrochemical impedance spectroscopy (EIS). Based on the low-frequency region of the Nyquist plot, the hydrogen ion diffusion coefficient could be calculated using the following equation.

[0191] D = 0.5(RT / An) 2 F 2 σ w C) 2 (4)

[0192] Where R is the gas constant, T is the absolute temperature, A is the electrode area, n is the number of electrons transferred per mole during the electrode reaction, F is the Faraday constant, and C is the H₂O concentration. + Concentration, σ w The Warburg factor can be obtained from Z' with respect to ω. -1 / 2 picture( Figure 9 The slope of e (illustration) is obtained. Therefore, the H of the MoO3 electrode + The diffusion coefficient was calculated to be 3.27 × 10⁻⁶. -10 cm 2 s -1 This is in very good agreement with the results obtained through CV (not shown), which is Li + (1.09×10 -11 cm 2 s -1 It is 30 times higher than that of H in all discharge states. + The Warburg factor is much smaller than that of Li. + This indicates the ultrafast diffusion kinetics of hydrogen ions during the cycling process. The ion diffusion coefficient of hydrogen ions in the MoO3-nanofiber electrode was calculated using the Randles-Sevcik equation and CV measurements. The apparent ion diffusion coefficient D at the peaks of Al, A2, C1, and C2 is... CV The calculated values ​​are 2.00 × 10⁻⁶. -10 3.41×10 -10 2.10×10 -10 and 4.71×10 - 10 cm 2 s -1 Therefore, the average ion diffusion coefficient obtained by CV is 3.06 × 10⁻⁶. -10 cm 2 s -1 .

[0193] Based on low area loading (1 mg cm⁻¹) -2 The attractive electrochemical properties of thick electrodes were investigated to study their charge storage performance. Electrodes with high areal loading (from 8.43 to 90.48 mg / cm²) were prepared by coating both sides of carbon fiber paper. -2 ). 90.48mg cm -2 The value represents the highest loading achieved using the aforementioned conventional coating method, and is considered to be the highest area loading reported to date. Electrode thickness, excluding the carbon fiber paper, ranges from 0.14 to 1.52 mm. Figure 10 a). In Figure 11 The figure shows 49mg cm -2 The selection of cross-sectional mapping images of the electrode, where MoO3 is uniformly distributed on both sides of a 933.3 μm thick carbon fiber paper. The high area loading electrode was then subjected to an 18 mA cm⁻¹... -2 Constant current charging and discharging, 18mA cm -2 It is considered to be the highest areal current density in the battery development community to date. Figure 11 b). Even at such a high current density, 90.48 mg cm⁻¹ -2 The electrodes also exhibited a capacity of 14.9 mAh cm⁻¹. -2 Its high area capacity is far higher than that of reported lithium-ion and sodium-ion batteries (<10mAh cm⁻¹). -2 To illustrate the linear relationship between areal capacity and active material loading, the high capacity of the first cycle was subtracted. The linear relationship was confirmed using a thickness versus areal loading plot. Figure 10 This indicates that hydrogen ions can still diffuse through a thick electrode despite a relatively long transport distance. Furthermore, at the same gravimetric current density, electrodes with different areal loadings can provide very similar specific capacities. Figure 11 c).

[0194] In addition to excellent capacity, thick electrodes also exhibit excellent rate performance and long-cycle stability. Figure 11 d) This is rare for high-loading electrodes. At 6A g -1 Achieving 147mAh g at a high current density (30C) was achieved. -1 Its high capacity was maintained at 0.6A g. -1 (3C) 67% of the capacity. Stability after long-term current fluctuations was further evaluated; even after 5000 cycles at 25C, 87% of the capacity was retained, corresponding to a small capacity decay of 0.003% per cycle. Notably, the thickness of the high-load electrode changed negligibly before and after cycling. Figure 12This demonstrates the structural stability of MoO3 when storing small-sized hydrogen ions and further explains the observed excellent cycling stability.

[0195] like Figure 11 As shown in e, the MoO3 anode for hydrogen ion storage / intercalation has a capacity of up to 22.4 mAh cm⁻¹. -2 The high areal capacity is considered superior to most (if not all) energy storage devices reported to date, including lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), lithium-sulfur batteries (Li-S), lithium-ion microcells (LIMBs), and supercapacitors. Furthermore, the embodiments reported herein utilize conventional coating methods for electrode fabrication without relying on any special modifications. Therefore, this method can be considered a more attractive option for industrial manufacturing and large-scale applications.

[0196] in conclusion

[0197] Example 2 demonstrates that hydrogen ions can completely diffuse into the thick electrode to achieve an ultra-high areal capacity. With a relatively low areal loading, a capacity of 235 mAh g⁻¹ can be achieved at 5C using a MoO₃ nanofiber anode. -1 Its high specific capacity, and impressive rate performance up to 200C. This high specific capacity is attributed to H during cycling. 2.0 MoO3 and H 1.1 Reversible redox reactions occur between MoO3 molecules. Notably, the high areal loading electrode also exhibits excellent rate performance, long lifetime (e.g., ≥5000 cycles), and a 22.4 mAh / cm³ capacity. -2 Its ultra-high areal capacity. Dynamic studies reveal that the calculated H... + Diffusion coefficient (3.27×10) -10 cm 2 s -1 ) is Li + (1.09×10 -11 cm 2 s -1 It is 30 times higher than that of conventional coating methods. High-load electrodes can be achieved through conventional coating methods, which enables a simple battery assembly process and reduces costs, which is beneficial for industrial manufacturing and large-scale applications.

[0198] Example 3

[0199] Mn-H batteries / cells were fabricated. In this example, the battery used MoO3 (prepared in the same manner as in Example 2) as a material capable of absorbing protons and / or hydrated hydrogen ions, MnO2 as the positive electrode material, and Mn... 2+ As a reducing positive electrode material (i.e., the redox pair MnO2 / Mn 2+The redox pair is introduced into the system (the electrolyte is aqueous and contains Mn). 2+ ).

[0200] exist Figure 17 The diagram depicts a schematic of the battery, showing the positive electrode process (left-hand side), the negative electrode process (right-hand side), and the chemical structure and electrolyte content of the expected Mo complex.

[0201] The electrochemical properties of the battery were evaluated in standard laboratory-grade glassware (sealed beaker-type and H-type cells). Typically, a 4x4cm piece of glassware was used. 2 A carbon felt (approximately 6 mm thick) is used as the positive electrode current collector, with a 2*1 cm piece... 2 A Ti substrate (plate or mesh) is used as the negative electrode current collector, with the negative electrode (average ~5mg) loaded at a 1*1cm² surface. 2 The working area was used, and 0.8M MnSO4 in 4.4M H2SO4 was used as the electrolyte. Once the battery cell was fabricated, two-electrode tests were performed under different test conditions using a Landt battery tester.

[0202] Custom-designed battery equipment was used, and... Figure 19 An exploded view of the battery assembly is shown, and... Figure 20a The image shows a photograph of the assembled battery.

[0203] Battery performance was also tested using a custom-designed battery device. In the experiment, carbon felt (4*4cm) was used. 2 (2 layers), load capacity 4*4cm 2 18.97 mg MoO3 and 40 mL of the above-mentioned mixed electrolyte were used on a Ti network. The results of these tests are summarized in... Figure 20b -c. Using a similar configuration, higher capacity can be obtained when the loading mass of the active material (41.81 mg) is increased, such as... Figure 20d As shown.

[0204] In summary, the results show that the battery has high energy efficiency, ultra-high power density and good cycle stability.

[0205] It should be understood that if any prior art publications are cited in this document, such reference does not imply an admission that such publications constitute part of common general knowledge in the field, in Australia, or in any other country.

[0206] In the appended claims and the preceding description of the invention, unless the context otherwise requires it due to the language of expression or necessary implication, the word “comprising” or variations such as “including” or “containing” are used in an inclusive sense, indicating the presence of the indicated feature in the various embodiments of the invention, but not excluding the presence or addition of other features.

Claims

1. A battery comprising: - a positive electrode, - an electrolyte, the electrolyte being capable of conducting protons and / or hydronium ions; and - a negative electrode, the negative electrode comprising an electrically conductive substrate coated with a layer comprising a material capable of absorbing protons and / or hydronium ions and a polymer electrolyte binder; wherein: (i) the electrolyte comprises a reduced form of a positive electrode species; or (ii) the positive electrode is in contact with a positive electrode species and the electrolyte comprises a reduced form of a positive electrode species, and the positive electrode species is an oxide or oxide of halide of one or more metals.

2. The battery of claim 1, wherein the positive electrode species is an oxide of Mn, Pb, Bi, Cr, V, Cl, Br, or I.

3. The battery of claim 1 or 2, wherein 5. The battery of claim 1 or 2, wherein the material capable of absorbing protons and / or hydronium ions is selected from the group consisting of N,N-dioctyl-3,4,9,10- perylene dicarboximide (PTCDI), perylene tetracarboxylic diimide (PTCDA), 1,4,5,8- naphthalene tetracarboxylic diimide (NTCDA), terephthalic acid (PTA), anthraquinone (AQ), and pyrene-4,5,9,10-tetraone (PTO). - the positive electrode material is Mn02, and the reduced positive electrode material is Mn 2+ ; or - the positive electrode material is MnO4 - and the reduced positive electrode material is MnO2; or - the positive electrode material is PbO2, and the reduced positive electrode material is Pb 2+ ; or - the positive electrode material is Bi2O4, and the reduced positive electrode material is BiO + ; or - the positive electrode material is Cr2O7 2- , and the reduced positive electrode material is Cr 3+ ; or - the positive electrode material is V02 + , and the reduced positive electrode material is V0 2+ ; or - the positive electrode material is CIO4 - , and the reduced positive electrode material is CIO3 - ; or - the positive electrode material is BrO3 - and the reduced positive electrode material is Br2; or - the positive electrode material is IO3 - and the reduced positive electrode material is I2.

4. The battery according to claim 1 or 2, wherein the positive electrode material is Mn02, and the reduced positive electrode material is Mn 2+ .

6. The battery of claim 1 or 2, wherein the positive electrode comprises a current collector selected from the group consisting of carbon cloth, carbon fiber paper, carbon felt, and combinations thereof.

7. The battery of claim 1 or 2, wherein the electrically conductive substrate of the negative electrode comprises one or more of carbon cloth, carbon fiber paper, carbon felt, titanium foil, and titanium mesh in contact with the material capable of absorbing protons and / or hydronium ions.

8. The battery of claim 1 or 2, wherein the battery comprises a separator selected from the group consisting of a nafion polymer membrane, a glass fiber membrane, a filter paper, and a Cagle membrane.

9. The battery of claim 1 or 2, wherein the material capable of absorbing protons and / or hydronium ions is MoO3, or the material capable of absorbing protons and / or hydronium ions comprises MoO3.

10. The battery of claim 1 or 2, wherein the material capable of absorbing protons and / or hydronium ions is MoO3 nanofibers, or the material capable of absorbing protons and / or hydronium ions comprises MoO3 nanofibers.

11. The battery of claim 1 or 2, wherein the polymer electrolyte binder is selected from the group consisting of nafion, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethylcellulose (CMC), sulfonated polyether ether ketone (SPEEK), and combinations thereof.

12. The battery of claim 1 or 2, wherein the layer coating the electrically conductive substrate further comprises an additive selected from the group consisting of acetylene black, XC-72R, and combinations thereof.

13. A method of manufacturing a battery, the method comprising contacting an electrolyte with a negative electrode and a positive electrode, wherein: ​ - the electrolyte is capable of conducting protons and / or hydronium ions and comprises (a) protons and / or hydronium ions and (b) a reduced positive electrode material, the conjugated redox pair of which is a positive electrode material that is an oxide of an oxide or halide of one or more metals; and - the negative electrode comprises an electrically conductive substrate and a material capable of absorbing protons and / or hydronium ions in contact with the electrically conductive substrate, wherein the material is brought into contact with the electrically conductive substrate by applying a fluid comprising the material, a polymeric electrolyte binder and a solvent onto the electrically conductive substrate to form a layer coated thereon.

14. The method of claim 13, wherein the method further comprises the step of depositing the positive electrode material on the positive electrode.

15. The method of claim 13 or 14, wherein the method comprises associating protons and / or hydronium ions with the material capable of absorbing protons and / or hydronium ions.

16. The method of claim 13 or 14, wherein the fluid is applied onto the electrically conductive substrate by a method involving one or more of spray coating, roll-to-roll coating, slot-die coating, ultrasonic brushing and doctor blading.

17. The method of claim 13 or 14, wherein the polymeric electrolyte binder is selected from the group consisting of nafion, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethylcellulose (CMC), sulfonated polyether ether ketone (SPEEK) and combinations thereof.

18. The method of claim 13 or 14, wherein the solvent is 2-propanol.

19. The method of claim 13 or 14, wherein the fluid comprising the material further comprises an additive selected from acetylene black, XC-72R and combinations thereof.

20. The method of claim 13 or 14, wherein the fluid comprising the material is in the form of a slurry.

21. A battery manufactured by the method of any one of claims 13 to 20.

22. Use of the battery of any one of claims 1 to 12 or 21 for energy storage.

23. A method of splitting water without releasing gaseous hydrogen or gaseous oxygen, the method comprising: - applying a voltage between the negative and positive electrodes of the battery as described in any one of claims 1 to 12 or 21, thereby oxidizing the reduced positive electrode material, forming positive electrode material and H + , the H + forming hydronium ions associated with the material capable of absorbing hydronium and / or water molecules, wherein the positive electrode material is an oxide of an oxide or halide of one or more metals.

24. A battery comprising: - a positive electrode capable of absorbing and releasing protons and / or hydronium ions, - an electrolyte capable of conducting protons and / or hydronium ions; and - a negative electrode comprising an electrically conductive substrate coated with a layer comprising a material capable of absorbing protons and / or hydronium ions and a polymeric electrolyte binder, wherein the material capable of absorbing protons and / or hydronium ions is MoO3, or the material capable of absorbing protons and / or hydronium ions comprises MoO3, and 24. The battery of claim 23, wherein the positive electrode material is MoO3. wherein the polymer electrolyte binder is selected from the group consisting of nafion, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), sulfonated polyether ether ketone (SPEEK), and combinations thereof; wherein, (i) the electrolyte comprises a reduced positive electrode material; or (ii) the positive electrode is in contact with a positive electrode material and the electrolyte comprises a reduced positive electrode material, and wherein, in use, protons and / or hydronium ions move between the positive electrode and the negative electrode.

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