Aluminum-manganese battery using aluminum hydride or dehydrogenation product thereof as negative electrode

Abstract

The present invention relates to the technical field of aluminum batteries, and discloses an aluminum-manganese battery using an aluminum hydride or a dehydrogenation product thereof as a negative electrode, the aluminum-manganese battery comprises an aluminum-based negative electrode material, a manganese-based positive electrode material, an electrolyte and a diaphragm, and the aluminum-based negative electrode material adopts the aluminum hydride or the dehydrogenation product of the aluminum hydride. According to the aluminum-manganese battery provided by the invention, the aluminum hydride and the product after dehydrogenation of the aluminum hydride are used as the negative electrode, so that the problem that a traditional aluminum negative electrode is easy to grow dendritic crystals can be relieved, and high energy density, excellent cycle performance and intrinsic safety are realized by combining the high-stability ionic liquid electrolyte and the high-capacity manganese-based positive electrode; meanwhile, lithium resource limitation and electrolyte flammable risks are avoided, an innovative technical scheme is provided for low cost and sustainable energy storage, and high-valued utilization of a dehydrogenated product with a specific microstructure generated after hydrogen release through thermal decomposition of the aluminum hydride is achieved.

Description

Technical Field

[0001] This invention relates to the field of aluminum battery technology, and specifically to a new aluminum battery system: aluminum-manganese battery. Background Technology

[0002] Due to aluminum's low cost, low flammability, and three-electron redox properties, rechargeable aluminum-based batteries theoretically offer cost-effectiveness, high capacity, and safety. Therefore, aluminum-ion batteries have broad application prospects in next-generation large-scale energy storage systems.

[0003] Traditional aluminum-ion batteries use aluminum as the negative electrode, which presents several problems: dendrites easily form during charging, potentially piercing the separator and causing internal short circuits, posing safety hazards; a dense aluminum oxide passivation film naturally forms on the surface, hindering the transport of aluminum ions and electrons, increasing internal resistance, reducing voltage and efficiency, and affecting charge-discharge performance and cycle stability. Aluminum hydride, as a high-capacity hydrogen storage material, has been widely studied in non-battery fields (such as on-board hydrogen storage). One of its core applications is the thermal decomposition to release hydrogen (2·AlH3→·2·Al·+·3·H2) for use in fuel cells. Typically, the thermal decomposition of aluminum hydride to release hydrogen produces waste aluminum powder or other related byproducts. However, research has found that these in-situ generated products possess the following characteristics: a highly porous structure, extremely large specific surface area, high purity, and virtually no oxide layer on the surface.

[0004] Meanwhile, traditional aluminum-ion battery cathode material systems also have limitations: graphite carbon materials and Prussian blue analogues suffer from low specific capacity, restricting energy density improvement, while transition metal sulfides face bottlenecks such as poor cycle stability, weak rate performance, and large charge / discharge volume expansion. Patent CN 116598482 A discloses a conversion-type cathode material for aluminum batteries, in which low-valence metal ions (liquid phase) rapidly diffuse in molten salt and deposit as high-valence solid compounds. This liquid-solid conversion reaction breaks through the fast-charging bottleneck. However, because the solubility of the cathode material changes significantly with temperature, its capacity is limited at low temperatures, thus restricting battery performance. In comparison, manganese-based materials offer a solution due to their multiple advantages: manganese resources are abundant, and the cost of ore mining and processing is far lower than that of key metals such as lithium, cobalt, and nickel; manganese has excellent environmental compatibility (non-toxic / low-toxic), and its oxide matrix is ​​not easily flammable or explosive. Combined with aluminum anodes and non-flammable electrolytes, aluminum-manganese battery systems theoretically offer higher safety; and its polymorphic structure (α / β / γ / δ / ε) forms diverse intercalation channels, providing a suitable environment for Al… 3+Efficient insertion / extraction provides unique sites; manganese dioxide possesses both a high theoretical capacity of 308 mAh / g and a high operating voltage. These indicate that designing novel batteries using manganese-based materials has broad application prospects. Yu et al. (He, S. et al. A High-Energy Aqueous Aluminum-Manganese Battery. Adv. Funct. Mater. 2019, 29, 1905228, 1–9.) mentioned assembling an aqueous aluminum-manganese battery and pre-adding Mn to the electrolyte. 2+ This study improved the battery's energy density and cycle stability, but it also has some limitations: insufficient cycle life (the battery only cycled stably for 65 times with a capacity retention of approximately 58%); and limited rate performance (at a high current density of 300 mA g). -1 The capacity dropped sharply to 125 mAh g. -1 The electrolyte concentration window is narrow, and Mn 2+ The concentration added must be strictly controlled at 0.5 M; deviations from this value will lead to capacity decay or precipitation. These issues limit its application. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of this invention is to provide an aluminum-manganese battery that uses aluminum hydride or its dehydrogenation product as the negative electrode. This novel battery system can achieve high energy density, excellent cycle performance and intrinsic safety, while avoiding the limitations of lithium resources and the risk of electrolyte flammability, providing an innovative technical solution for low-cost and sustainable energy storage.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: The present invention provides an aluminum-manganese battery using aluminum hydride or its dehydrogenated product as the negative electrode, comprising an aluminum-based negative electrode material, a manganese-based positive electrode material, an electrolyte, and a separator. The aluminum-based negative electrode material is an aluminum hydride or its dehydrogenated product.

[0007] Further: the aluminum hydride includes one or more of AlH3, LiAlH4, NaAlH4, KAlH4, Mg(AlH4)2, Ca(AlH4)2, LiMg(AlH4)3, and K2NaAlH6; the dehydrogenation products of the aluminum hydride include one or more of Al obtained from the dehydrogenation of AlH3, LiH obtained from the dehydrogenation of LiAlH4, NaH obtained from the dehydrogenation of NaAlH4, KH obtained from the dehydrogenation of KAlH4, MgH2 obtained from the dehydrogenation of Mg(AlH4)2, and CaH2 obtained from the dehydrogenation of Ca(AlH4)2. Most preferably: the aluminum hydride is AlH3 or LiAlH4; the dehydrogenation products of the aluminum hydride include aluminum powder obtained from the dehydrogenation of AlH3. The negative electrode material provided by this invention possesses a high theoretical specific capacity, and the dehydrogenation process forms a nanoporous aluminum structure in situ, significantly improving the reactive sites and ion diffusion efficiency, while effectively suppressing aluminum dendrite growth through uniform current distribution. In particular, by pioneering the use of aluminum hydride dehydrogenation products as the negative electrode, the cost and energy consumption of recycling and remelting or specially preparing highly active aluminum powder are eliminated, thus finding a high-value application outlet for waste by-products.

[0008] Further, the manganese-based cathode material is a manganese oxide, including one or more of α-MnO2, β-MnO2, γ-MnO2, λ-MnO2, δ-MnO2, and ε-MnO2, with γ-MnO2 or δ-MnO2 being the most preferred. The cathode material provided by this invention has diverse crystal structures (tunnel / layered / spinel) and is Al 3+ Embedding provides an efficient diffusion channel, while manganese is abundant, environmentally friendly, and combines low cost with high stability.

[0009] Furthermore, the electrolyte is an ionic liquid electrolyte. The ionic liquid electrolyte is an AlCl3-[EMIM]Cl ionic liquid composed of AlCl3 and 1-ethyl-3-methylimidazolium chloride in a molar ratio of 1.1~1.8:1 (preferably 1.3:1). The electrolyte provided by this invention has a wide electrochemical window, and its non-flammable and non-volatile properties solve safety hazards; through Al2Cl7... - / AlCl4 - Isocoordination structure achieves high efficiency Al 3+ It conducts and forms a stable SEI film over a wide temperature range, significantly improving coulombic efficiency and cycle life.

[0010] Furthermore, the separator comprises one or more of the following: polyolefin microporous membrane, ceramic-coated membrane, nonwoven membrane, and glass fiber membrane. Preferably, it is a glass fiber membrane, which possesses high thermal stability and chemical inertness (resisting strong acid / alkali corrosion), good electrolyte affinity (the microfiber network enables rapid liquid absorption and long-term liquid retention, reducing battery internal resistance), and a three-dimensional high-porosity structure, meeting the requirements for high safety, corrosion resistance, and electrolyte stability.

[0011] Furthermore, the preparation process of the aluminum-manganese battery is carried out under the protection of an inert gas. The inert gas is selected from any one or more of ultra-dry nitrogen, ultra-dry argon and ultra-dry helium. The purity of the gas used is ≥99.999% and the water content is ≤5 ppm to ensure an anhydrous and oxygen-free state during the preparation process.

[0012] Compared with the prior art, the technical solution of the present invention has at least the following beneficial effects: This invention provides a novel aluminum-manganese battery that innovatively employs aluminum hydride and its dehydrogenation products as the negative electrode, while cleverly combining a highly stable and safe ionic liquid electrolyte with a low-cost, high-capacity manganese oxide positive electrode to construct a completely new secondary battery system. This system boasts significant advantages such as high theoretical energy density, high intrinsic safety, abundant raw materials, low cost, and environmental friendliness. It effectively alleviates the problem of dendrite growth in traditional aluminum negative electrodes, while avoiding the safety hazards of lithium resource limitations and the flammability of electrolytes. This provides a competitive technological route for next-generation high-performance, low-cost, safe, and sustainable energy storage technologies. Furthermore, this invention can directly use the dehydrogenation products of aluminum hydride as the negative electrode, eliminating the cost and energy consumption of recycling and remelting or specially preparing highly active aluminum powder, thus finding a high-value application outlet for waste byproducts. Attached Figure Description

[0013] Figure 1 The image shows the XRD pattern of AlH3 in Example 1. Figure 2 Here is a SEM image of AlH3 in Example 1; Figure 3 The Raman spectrum of the AlCl3-[EMIM]Cl ionic liquid prepared in Example 1 is shown below. Figure 4 The image shows the XRD pattern of γ-MnO2 in Example 1. Figure 5 Here is a SEM image of γ-MnO2 in Example 1; Figure 6 The cyclic voltammetry curves of the aluminum-manganese battery prepared in Example 1 at a scan rate of 0.4 mV / s are shown. Figure 7The constant current charge-discharge curves of the aluminum-manganese battery prepared in Example 1 at a current density of 0.05 A / g for the 1st, 2nd, 10th, and 50th cycles are shown. Figure 8 The image shows the XRD pattern of the aluminum powder prepared in Example 2. Figure 9 The cyclic voltammetry curves of the aluminum-manganese battery prepared in Example 2 at a scan rate of 0.4 mV / s are shown. Figure 10 The constant current charge-discharge curves of the aluminum-manganese battery prepared in Example 2 at a current density of 0.05 A / g for the first three cycles are shown. Figure 11 The XRD pattern of δ-MnO2 prepared in Example 3; Figure 12 This is a SEM image of δ-MnO2 obtained in Example 3; Figure 13 The cyclic voltammetry curves of the aluminum-manganese battery prepared in Example 3 at a scan rate of 0.4 mV / s are shown. Figure 14 The constant current charge-discharge curves of the aluminum-manganese battery prepared in Example 3 at a current density of 0.1 A / g for the first five cycles are shown. Figure 15 The cyclic voltammetry curves of the aluminum-manganese battery prepared in Example 4 are shown at a scan rate of 0.4 mV / s. Figure 16 The image shows the XRD pattern of LiAlH4 in Example 5. Figure 17 Here is a SEM image of LiAlH4 in Example 5; Figure 18 The cyclic voltammetry curves of the aluminum-manganese battery prepared in Example 5 at a scan rate of 0.8 mV / s are shown. Figure 19 The cyclic voltammetry curves of the aluminum-manganese battery prepared in Example 6 at a scan rate of 0.4 mV / s are shown. Figure 20 The constant current charge-discharge curves of the aluminum-manganese battery prepared in Example 6 at a current density of 0.1 A / g for the first three cycles are shown. Figure 21 The aluminum-aluminum symmetric cell prepared in Example 7 operates at 0.06369 mA / cm². -2 Deposition of 0.025 mAh cm⁻¹ at current density -2 Long-cycle curve of aluminum; Figure 22 This is a SEM image of the electrode material prepared in Example 7 before cycling; Figure 23 SEM image of the electrode material prepared in Example 7 after cycling; Figure 24 The constant current charge-discharge curves of the aluminum-manganese battery prepared in Comparative Example 1 at a current density of 0.05 A / g are shown for the first three cycles. Figure 25 The constant current charge-discharge curves for the first three cycles of the aluminum-manganese battery prepared in Comparative Example 2 at a current density of 0.05 A / g are shown. Detailed Implementation

[0014] To better understand the technical solution of the present invention, the embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0015] Example 1 This embodiment provides an aluminum-manganese battery, comprising an aluminum-based negative electrode material, a manganese-based positive electrode material, an electrolyte, and a separator. The specific preparation steps are as follows: 1. Preparation of negative electrode sheet The negative electrode material uses aluminum hydride (AlH3) powder, and its XRD and SEM images are shown below. Figure 1 and Figure 2 As shown. Figure 1 As shown, AlH3 exhibits distinct diffraction peaks at specific diffraction angles, which largely coincide with the theoretical peak positions on the standard PDF card. The sharp and high-intensity diffraction peaks indicate good crystallinity, and the absence of diffuse broadening peaks suggests a large grain size and few defects. Figure 2 As shown, AlH3 exhibits a multicubic aggregate structure.

[0016] Take an appropriate amount of the aluminum hydride, put it into a mold, and then place it on an automatic powder tablet press to obtain a negative electrode sheet with a diameter of 10 mm.

[0017] 2. Preparation of electrolyte 1-Ethyl-3-methylimidazolium chloride was vacuum dried at 130°C for 16 hours to remove residual moisture. Anhydrous aluminum chloride and 1-ethyl-3-methylimidazolium chloride were mixed at a molar ratio of 1.3:1 in a glove box under ultra-dry nitrogen protection. The mixture was stirred at room temperature for 20 minutes and then ultrasonically mixed to obtain a light yellow, transparent AlCl3-[EMIM]Cl ionic liquid electrolyte, which was then allowed to stand for later use.

[0018] Figure 3 The Raman spectrum of the AlCl3[EMIM]Cl ionic liquid electrolyte obtained in this embodiment shows that AlCl4 - and Al2Cl7 - The presence of anions.

[0019] 3. Preparation of positive electrode sheet The cathode material used is γ-MnO2, and its XRD and SEM images are shown below. Figure 4 and Figure 5 As shown. Figure 4 As shown, the main diffraction peaks of γ-MnO2 appear at 22.4°, 37.1°, and 38.8°, belonging to the (1 2 0), (1 3 1), and (0 0 2) crystal planes, respectively. Figure 5 As shown, γ-MnO2 mainly exhibits a loosely packed network with a nanorod morphology and a tunnel structure.

[0020] The preparation method of the positive electrode sheet is as follows: weigh the positive electrode material, Ketjen black and polyvinylidene fluoride in a mass ratio of 6:3:1 and put them into an agate mortar. Add an appropriate amount of N-methyl-2-pyrrolidone and grind evenly to form a positive electrode slurry. Then coat it evenly on a titanium foil current collector and finally put it into an 80℃ vacuum oven to bake for 8 hours to make a positive electrode sheet.

[0021] 4. Assemble the battery Take the button cell casing and assemble the negative electrode sheet, AlCl3-[EMIM]Cl ionic liquid electrolyte, and positive electrode sheet obtained in the above steps into an aluminum-manganese battery. The separator is a glass fiber separator.

[0022] Figure 6 The cyclic voltammetry curves of the aluminum-manganese battery prepared in this embodiment at a scan rate of 0.4 mV / s show an oxidation peak at 0.74 V and a reduction peak at 0.45 V, indicating that the battery assembled with the positive and negative electrode materials used in this embodiment has good reversibility.

[0023] Figure 7 The graphs show the constant current charge-discharge curves of the aluminum-manganese battery prepared in this embodiment at a current density of 0.05 A / g for the 1st, 2nd, 10th, and 50th cycles. According to the charge-discharge curves, the overpotential of the battery is about 0.1 V. At a current density of 0.05 A / g, the charge-discharge specific capacities for the first cycle are 25.25 mAh / g and 15.84 mAh / g, respectively; for the second cycle, they are 24.47 mAh / g and 14.92 mAh / g, respectively; for the tenth cycle, they are 19.99 mAh / g and 11.57 mAh / g, respectively; and for the fiftieth cycle, they are 12.31 mAh / g and 8.77 mAh / g, respectively.

[0024] Example 2 This embodiment prepares an aluminum-manganese battery using the same method as in Example 1, the only difference being that the negative electrode material used is aluminum powder obtained from the dehydrogenation of AlH3, and its XRD pattern is shown below. Figure 8As shown, the preparation method is as follows: take an appropriate amount of AlH3 powder, heat it at 180℃ for 1 hour under inert gas protection to decompose and release hydrogen, and obtain dehydrogenated aluminum powder. The reaction formula is 2·AlH3→·2·Al·+·3·H2.

[0025] Figure 9 The image shows the cyclic voltammetry curves of the aluminum-manganese battery prepared in this embodiment at a scan rate of 0.4 mV / s. The test results show an oxidation peak at 0.65 V (corresponding to aluminum ion insertion) and a reduction peak at 0.47 V (corresponding to aluminum ion deposition). The peak positions in the first, second, and third cycles do not show significant shifts, indicating that the battery assembled using the positive and negative electrode materials used in this embodiment has good reversibility.

[0026] Figure 10 The images show the constant current charge-discharge curves of the aluminum-manganese battery prepared in this embodiment at a current density of 0.05 A / g for the first three cycles. According to the charge-discharge curves, the battery has an overpotential of approximately 0.08 V and exhibits a clear charge-discharge voltage plateau. At a current density of 0.05 A / g, the charge-discharge specific capacities for the first cycle are 114 mAh / g and 152.67 mAh / g, respectively; for the second cycle, they are 104.54 mAh / g and 134.51 mAh / g, respectively; and for the third cycle, they are 99.01 mAh / g and 120.64 mAh / g, respectively.

[0027] Example 3 This embodiment prepared an aluminum-manganese battery using the same method as in Example 2, the only difference being that the positive electrode material used was δ-MnO2. The preparation method was as follows: 240 mg of potassium permanganate and 40 mg of manganese sulfate monohydrate were added to 60 mL of deionized water and stirred for 30 minutes to ensure thorough mixing of the raw materials. The solution was then transferred to a polytetrafluoroethylene-coated stainless steel high-pressure reactor and heated at 160°C for 12 hours. After cooling to room temperature, the precipitate was centrifuged multiple times, washed successively with deionized water and ethanol, and then vacuum dried at 80°C for 12 hours to obtain δ-MnO2. The XRD and SEM images of the obtained δ-MnO2 are shown below. Figure 11 and Figure 12 As shown. Figure 11 As shown, the two main diffraction peaks of δ-MnO2 are located at 12.5° and 25.2°, corresponding to the (0 0 1) and (0 0 2) crystal planes, respectively.

[0028] Figure 13 The cyclic voltammetry curves of the aluminum-manganese battery prepared in this embodiment at a scan rate of 0.4 mV / s show that there is an oxidation peak at 0.65 V and a reduction peak at 0.41 V. The peak positions in the first, second and third cycles are not significantly shifted, indicating that the battery assembled with the positive and negative electrode materials in this embodiment has good reversibility.

[0029] Figure 14 The chart shows the constant current charge-discharge curves of the aluminum-manganese battery prepared in this embodiment at a current density of 0.1 A / g for the first five cycles. According to the curves, the battery has an overpotential of approximately 0.125 V and exhibits a clear charge-discharge voltage plateau, which roughly corresponds to the CV test results. At a current density of 0.1 A / g, the charge-discharge specific capacities for the first cycle are 24.75 mAh / g and 50.06 mAh / g, respectively; for the second cycle, 19.72 mAh / g and 39.41 mAh / g, respectively; for the third cycle, 16.45 mAh / g and 33.22 mAh / g, respectively; for the fourth cycle, 14.33 mAh / g and 29 mAh / g, respectively; and for the fifth cycle, 12.81 mAh / g and 26.04 mAh / g, respectively.

[0030] Example 4 This embodiment prepares an aluminum-manganese battery using the same method as in Example 3, the only difference being that the negative electrode material used is AlH3 powder.

[0031] Figure 15 The cyclic voltammetry curves of the aluminum-manganese battery prepared in this embodiment at a scan rate of 0.4 mV / s are shown.

[0032] Example 5 This embodiment prepares an aluminum-manganese battery using the same method as in Example 1, the only difference being that the negative electrode material used is LiAlH4 powder. Its XRD and SEM images are shown below. Figure 16 and Figure 17 As shown.

[0033] Figure 18 The image shows the cyclic voltammetry curves of the aluminum-manganese battery prepared in this embodiment at a scan rate of 0.8 mV / s.

[0034] Example 6 This embodiment prepares an aluminum-manganese battery using the same method as in Example 5, the only difference being that the positive electrode material used is δ-MnO2.

[0035] Figure 19 The cyclic voltammetry curves of the aluminum-manganese battery prepared in this embodiment at a scan rate of 0.4 mV / s are shown.

[0036] Figure 20The constant current charge-discharge curves of the aluminum-manganese battery prepared in this embodiment at a current density of 0.1 A / g are shown for the first three cycles. According to the charge-discharge curves, at a current density of 0.1 A / g, the charge-discharge specific capacities of the first cycle are 7.31 mAh / g and 24.35 mAh / g, the charge-discharge specific capacities of the second cycle are 6.81 mAh / g and 21.41 mAh / g, and the charge-discharge specific capacities of the third cycle are 6.5 mAh / g and 20.16 mAh / g, respectively. Example 7 In this embodiment, an aluminum-aluminum symmetric battery was prepared using the same method as in Example 2. The only difference was that the positive and negative electrode materials used were aluminum powder obtained by dehydrogenation of AlH3, and the assembled battery was an aluminum-aluminum symmetric battery.

[0037] Figure 21 The aluminum-aluminum symmetric cell prepared in this embodiment operates at 0.06369 mA / cm². -2 Deposition of 0.025 mAh cm⁻¹ at current density -2 Long-cycle curves of aluminum. The test results show that the polarization voltage is between 90 and 120 mV, the entire cycle reaches 1000 h without battery failure, and the voltage curve is basically symmetrical around the zero voltage line. This indicates that the ionic liquid electrolyte of this ratio can effectively support the deposition and stripping of aluminum under these conditions, and the process is highly reversible with good kinetic symmetry, demonstrating excellent cycle stability.

[0038] SEM images of the electrode material before and after cycling are shown below. Figure 22 and Figure 23 As shown, comparing the SEM images before and after the cycle, no dendrite growth was observed on the surface.

[0039] Comparative Example 1 This embodiment prepares an aluminum-manganese battery using the same method as in Example 2, the only difference being that the negative electrode material used is aluminum foil.

[0040] Figure 24The constant current charge-discharge curves for the aluminum-manganese battery prepared in this embodiment at a current density of 0.05 A / g are shown for the first three cycles. The test results show that the specific capacities for the first three cycles of the aluminum-manganese battery are (34.28 mAh / g, 74.23 mAh / g), (30.21 mAh / g, 67.94 mAh / g), and (31.11 mAh / g, 60.30 mAh / g). Based on the results of Example 2 and Comparative Example 1, the first-cycle discharge capacity of the aluminum powder anode reaches 152.67 mAh / g, more than twice that of the aluminum foil, proving that it can fully utilize the aluminum intercalation potential of γ-MnO2. The high specific surface area of ​​the aluminum powder promotes interfacial charge exchange with γ-MnO2, alleviating positive electrode polarization (the aluminum foil's positive electrode utilization is limited by interfacial passivation). The coulombic efficiency of the aluminum powder anode in the first cycle is far superior to that of the aluminum foil, and the dehydrogenated aluminum powder surface has virtually no oxide layer, avoiding excessive charge consumption in the first cycle.

[0041] Comparative Example 2 This embodiment prepares an aluminum-manganese battery using the same method as in Example 3, the only difference being that the negative electrode material used is aluminum foil.

[0042] Figure 25 The figures show the constant current charge-discharge curves of the aluminum-manganese battery prepared in this embodiment at a current density of 0.05 A / g for the first three cycles. The test results show that the specific capacity of this aluminum-manganese battery in the first charge-discharge cycle is only 1.18 mAh / g and 4.48 mAh / g, respectively. Based on the results of Example 3 and Comparative Example 2, the full-cell cycle performance of the embodiment of this invention using aluminum powder obtained through AlH3 dehydrogenation as the negative electrode material is significantly higher than that of the full-cell cycle performance using traditional aluminum foil as the negative electrode material. This indicates that the aluminum powder obtained through AlH3 dehydrogenation forms a nanoporous aluminum structure, significantly improving the reactive sites and ion diffusion efficiency.

[0043] Although the present invention has been illustrated and described with specific embodiments, it should be understood that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; those skilled in the art should understand that modifications can be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein, without departing from the spirit and scope of the present invention; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention; therefore, this means that all such substitutions and modifications that fall within the scope of the present invention are included in the appended claims.

Claims

1. An aluminum-manganese battery using aluminum hydride or its dehydrogenation product as the negative electrode, the aluminum-manganese battery comprising an aluminum-based negative electrode material, a manganese-based positive electrode material, an electrolyte, and a separator, characterized in that, The aluminum-based anode material is an aluminum hydride or a product of aluminum hydride dehydrogenation.

2. The aluminum-manganese battery according to claim 1, characterized in that, The aluminum hydride includes one or more of AlH3, LiAlH4, NaAlH4, KAlH4, Mg(AlH4)2, Ca(AlH4)2, LiMg(AlH4)3, and K2NaAlH6; the dehydrogenation products of the aluminum hydride include one or more of Al obtained by dehydrogenation of AlH3, LiH obtained by dehydrogenation of LiAlH4, NaH obtained by dehydrogenation of NaAlH4, KH obtained by dehydrogenation of KAlH4, MgH2 obtained by dehydrogenation of Mg(AlH4)2, and CaH2 obtained by dehydrogenation of Ca(AlH4)2.

3. The aluminum-manganese battery according to claim 2, characterized in that, The aluminum hydride is AlH3 or LiAlH4; the product after dehydrogenation of the aluminum hydride is aluminum powder obtained by dehydrogenation of AlH3.

4. The aluminum-manganese battery according to claim 1, characterized in that, The manganese-based cathode material is manganese oxide.

5. The aluminum-manganese battery according to claim 4, characterized in that, The manganese oxide is γ-MnO2 or δ-MnO2.

6. The aluminum-manganese battery according to claim 1, characterized in that, The electrolyte is an ionic liquid electrolyte.

7. The aluminum-manganese battery according to claim 6, characterized in that, The ionic liquid is an AlCl3-[EMIM]Cl ionic liquid composed of AlCl3 and 1-ethyl-3-methylimidazolium chloride in a molar ratio of 1.1 to 1.8:

1.

8. The aluminum-manganese battery according to claim 7, characterized in that, AlCl3 and 1-ethyl-3-methylimidazolium chloride were mixed at a molar ratio of 1.3:

1.

9. The aluminum-manganese battery according to claim 1, characterized in that, The diaphragm includes one or more of the following: polyolefin microporous membrane, ceramic-coated diaphragm, nonwoven fabric diaphragm, and glass fiber diaphragm.

10. An aluminum-manganese battery according to claim 1, characterized in that, The preparation process of the aluminum-manganese battery is carried out under the protection of an inert gas. The inert gas is selected from any one or more of ultra-dry nitrogen, ultra-dry argon and ultra-dry helium. The purity of the gas used is ≥99.999% and the water content is ≤5 ppm to ensure an anhydrous and oxygen-free state in the preparation process.

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