A cathode and an aluminum-ion battery
By optimizing the cathode material and electrolyte of aluminum-ion batteries, the corrosion and reversibility problems of aluminum-ion batteries have been solved, the energy density and power generation efficiency of the batteries have been improved, and reversible charge and discharge at medium and low temperatures have been achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-09
- Publication Date
- 2026-07-10
AI Technical Summary
Aluminum-ion batteries suffer from severe corrosion, significant hydrogen evolution due to self-corrosion, low energy density, and poor charge-discharge reversibility, resulting in low efficiency and high operating costs.
The composition of aluminum-ion batteries is optimized by using cathodes containing active materials such as manganese dioxide, ferric oxide, ferrous oxide, iron tetroxide, copper oxide, graphite, or metal carbonitride, combined with low co-solvent or molten salt electrolytes, including conductive agents and aluminum alloy anodes, and using a separator to isolate the anode and cathode.
It improves the power generation efficiency of aluminum-ion batteries, increases the energy density of batteries, reduces the operating temperature, improves the conductivity and ion mobility of electrolytes, achieves reversible charge and discharge, and reduces the viscosity coefficient.
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Figure CN122370299A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of battery technology, and in particular relates to a cathode and an aluminum-ion battery. Background Technology
[0002] Electrical energy is an important secondary energy source, but it is difficult to store for long periods. Electrical energy is stored in the form of supercapacitors and energy storage batteries, with materials including hydrogen, ammonia, methane, methanol, ethanol, carbon, silicon, and metals. Metals have the highest energy storage density; theoretically, lithium, aluminum, magnesium, calcium, titanium, sodium, potassium, iron, and zinc can all store more than 1000 Wh / kg of electrical energy. However, lithium resources are limited, making aluminum an important option for large-scale energy storage. Aluminum has a theoretical energy storage density of 8600 Wh / kg, and its voltage range is -1.66 to -2.35 volts, making it an excellent energy storage material. However, due to factors such as severe corrosion, low fuel utilization, hydrogen release, and oxide film passivation, aluminum still faces many challenges in its application as an energy storage material.
[0003] Currently, most aluminum-ion batteries are aqueous electrolyte batteries. Side reactions produce hydrogen gas, resulting in an efficiency of only 10-30% and a risk of explosion. Aqueous electrolyte aluminum batteries have low energy density and low power generation. Furthermore, the electrolyte is a strong alkaline solution, which is highly corrosive and places high demands on system materials. There is also the problem of severe electrolyte consumption, increasing operating costs. Some aluminum-ion batteries can only generate electricity and cannot be recharged, while those that can be charged and discharged have poor reversibility and high operating costs. Summary of the Invention
[0004] The present invention provides a cathode and an aluminum-ion battery, achieving at least one of the following objectives: overcoming at least one of the technical problems of aluminum-ion batteries, such as severe corrosion, severe self-corrosion and hydrogen evolution, low energy density, and poor reversibility of charge and discharge.
[0005] To achieve the above and other related objectives, the present invention provides the following technical solution:
[0006] In a first aspect, the present invention provides a cathode for an aluminum-ion battery, the cathode containing an active material, the active material being manganese dioxide, ferric oxide, ferrous oxide, magnetite, copper oxide, graphite, or a metal carbonitride, wherein the metal element includes at least one selected from gold, silver, copper, platinum, palladium, iron, cobalt, and nickel.
[0007] Furthermore, in the cathode of the aluminum-ion battery provided by the present invention, the graphite in the active material of the cathode is flake graphite or expanded graphite.
[0008] Furthermore, in the cathode of the aluminum-ion battery provided by the present invention, the content of metal elements in the graphite loaded with metal elements or the carbonitride metal is 1wt%-30wt%.
[0009] Furthermore, in the aluminum-ion battery cathode provided by the present invention, when the active material of the cathode is manganese dioxide, ferric oxide, ferrous oxide, magnetite, copper oxide, or metal carbonitride, the cathode also contains a conductive agent. Preferably, the conductive agent accounts for 20wt-50wt% of the mass of the active material.
[0010] Furthermore, in the cathode of the aluminum-ion battery provided by the present invention, the conductive agent is one of conductive graphite, graphene, carbon nanotubes, carbon black, and carbon fiber.
[0011] Furthermore, in the aluminum-ion battery cathode provided by the present invention, when the active material of the cathode is manganese dioxide, ferric oxide, ferrous oxide, iron oxide, copper oxide, or metal carbonitride, the active material is prepared into a slurry and coated on a graphite electrode to form the cathode.
[0012] In a second aspect, the present invention provides an aluminum-ion battery, wherein the cathode of the aluminum-ion battery is the cathode provided in the first aspect of the present invention.
[0013] Furthermore, the aluminum-ion battery provided by the present invention further includes an anode, the anode being made of aluminum or an aluminum alloy, wherein the aluminum alloy contains silicon. Preferably, the mass percentage of silicon in the aluminum alloy is 0.1 wt%-4.0 wt%.
[0014] Furthermore, the aluminum-ion battery provided by the present invention further includes an electrolyte, the electrolyte comprising a eutectic solvent system of aluminum chloride and organic components, the organic components comprising urea and / or triethylamine hydrochloride, wherein the molar ratio of aluminum chloride to organic components is 1:0.5-1.
[0015] Furthermore, in the aluminum-ion battery provided by the present invention, the electrolyte comprises aluminum chloride and triethylamine hydrochloride, wherein the molar ratio of aluminum chloride to triethylamine hydrochloride is 1.35:1 to 2.0:1.
[0016] Furthermore, in the aluminum-ion battery provided by the present invention, the electrolyte comprises aluminum chloride and urea, wherein the molar ratio of aluminum chloride to urea is 1.35:1 to 2.0:1.
[0017] Furthermore, the aluminum-ion battery provided by the present invention further includes an electrolyte, which comprises a molten salt system of aluminum chloride and chloride, wherein the chloride is at least one of lithium chloride, potassium chloride, and sodium chloride, and the mass percentage of aluminum chloride in the electrolyte is 40wt%-85wt%.
[0018] Furthermore, in the aluminum-ion battery provided by the present invention, the electrolyte comprises aluminum chloride, sodium chloride and potassium chloride, wherein the sodium chloride content is 8wt%-40wt% and the potassium chloride content is 3wt%-20wt%.
[0019] Furthermore, in the aluminum-ion battery provided by the present invention, the electrolyte contains aluminum chloride content of 40wt%-85wt%, potassium chloride content of 3wt%-20wt%, and lithium chloride content of 0-15wt%.
[0020] Furthermore, in the aluminum-ion battery provided by the present invention, the electrolyte contains 40wt%-85wt% aluminum chloride, 8wt%-40% sodium chloride, 3-20% potassium chloride, and 0-15% lithium chloride.
[0021] In a third aspect, the present invention provides a cylindrical aluminum-ion battery device, comprising the aluminum-ion battery described above, wherein the aluminum-ion battery includes an anode, a cathode, and an electrolyte disposed between the anode and the cathode;
[0022] The cylindrical aluminum-ion battery device also includes a cylindrical outer shell, the anode is disposed in the center of a cavity formed inside the outer shell, the cathode is coated on or attached to the inner wall of the outer shell, and the electrolyte is filled in the cavity of the outer shell.
[0023] Preferably, the aluminum-ion battery further includes a separator disposed between the aluminum anode and the air cathode.
[0024] Preferably, the diaphragm is disposed close to the cathode.
[0025] The aluminum-ion battery provided by this invention is a secondary battery. The cathode and anode are connected to the negative and positive terminals of an external power source, respectively, for charging. After charging, the cathode and anode are connected to the negative and positive terminals of a load, respectively, for discharging. The battery can be recharged after discharging and reused.
[0026] The beneficial effects of this invention are:
[0027] This invention employs a low-cosolvent electrolyte or a molten salt electrolyte, avoiding the generation of hydrogen gas in the side reactions of aqueous electrolytes and improving the power generation efficiency of aluminum. Simultaneously, the molten salt electrolyte or low-cosolvent electrolyte of this invention has a high electrochemical window, enabling reversible charge-discharge of aluminum-ion batteries.
[0028] The cathode material provided by this invention can increase the specific capacity of the battery and improve its energy density.
[0029] The cathode material and low-temperature molten salt electrolyte of this invention can reduce the operating temperature of aluminum-ion batteries from 130°C-250°C to 55-176°C, thereby reducing the viscosity coefficient and improving the conductivity and ion mobility of the electrolyte. Attached Figure Description
[0030] Figure 1 This is a schematic diagram of the structure of a cylindrical aluminum-ion battery device according to an embodiment of the present invention.
[0031] Figure 2 This is a charge-discharge curve diagram of the aluminum-ion battery involved in Embodiment 4 of the present invention.
[0032] Figure 3 This is a discharge specific capacity diagram of the aluminum-ion battery involved in Embodiment 4 of the present invention.
[0033] Figure 4 This is a charge-discharge cycle efficiency diagram of the aluminum-ion battery involved in Embodiment 4 of the present invention.
[0034] Figure 5 This is a charge-discharge curve diagram of the aluminum-ion battery involved in Embodiment 5 of the present invention.
[0035] Figure 6 This is a charge-discharge curve diagram of aluminum-ion batteries with different ferrous oxide contents in the cathode according to Embodiment 6 of the present invention.
[0036] Figure 7 This is a rate cycling diagram of an aluminum-ion battery with 30 wt% ferrous oxide doped in the cathode, as described in Example 6 of the present invention. Detailed Implementation
[0037] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification.
[0038] It should be understood that the structures, proportions, sizes, etc., illustrated in the accompanying drawings are merely for illustrative purposes to aid those skilled in the art and to facilitate understanding and reading. They are not intended to limit the implementation conditions of the invention and therefore have no substantial technical significance. Any modifications to the structure, changes in proportions, or adjustments to the size, without affecting the effectiveness and objectives of the invention, should still fall within the scope of the technical content disclosed in the invention. Furthermore, the terms "first," "second," and "third" in this specification are used for descriptive purposes only and should not be construed as indicating or implying relative importance.
[0039] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.
[0040] An embodiment of the present invention provides an aluminum-ion battery, including an anode, a cathode, and an electrolyte disposed between the anode and the cathode. The cathode contains an active material, which is manganese dioxide, ferric oxide, ferrous oxide, magnetite, graphite, copper oxide, graphite loaded with a metal element, or metal carbonitride. The metal element includes at least one selected from gold, silver, copper, platinum, palladium, iron, cobalt, and nickel.
[0041] In this invention, when the active material of the cathode is manganese dioxide, iron oxide, ferrous oxide, copper oxide, or metal carbonitride, a conductive agent also needs to be added to the cathode. The conductive agent can be selected from conductive graphite, graphene, carbon nanotubes, carbon black, and carbon fiber; this invention does not impose any particular limitation. In one embodiment of this invention, the amount of conductive agent added accounts for 20wt%-50wt% of the mass of the active material.
[0042] In this invention, when the active material of the cathode is manganese dioxide, iron oxide, ferrous oxide, copper oxide or metal carbonitride, the active material is prepared into a slurry and coated onto a graphite electrode to form a cathode.
[0043] In this invention, when the active material of the cathode is graphite or graphite loaded with metal elements, these active materials are themselves conductive, and there is no need to add a conductive agent to the cathode.
[0044] In one embodiment of the present invention, the graphite in the active material of the cathode is flake graphite or expanded graphite.
[0045] The cathode material provided by this invention can increase the specific capacity of the battery and improve its energy density.
[0046] In one embodiment of the present invention, the above-mentioned cathode active material or a mixture of cathode active material and conductive agent is pressed into a film to serve as a cathode; or the cathode active material is coated onto a graphite electrode to obtain a cathode. In other embodiments, other conventional preparation methods can also be used to prepare the above-mentioned cathode active material into a cathode.
[0047] In one embodiment of the present invention, the metal element doping amount in the graphite or metal carbonitride loaded with metal elements is 1wt%-30wt%, that is, the metal content in the graphite or metal carbonitride loaded with metal elements is 1wt%-30wt%. Typical but non-limiting metal element doping amounts in the present invention are 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, or 30wt%.
[0048] In this invention, the carbonitride metal includes, but is not limited to, at least one selected from gold carbonitride, silver carbonitride, copper carbonitride, platinum carbonitride, palladium carbonitride, iron carbonitride, cobalt carbonitride, and nickel carbonitride. Preferably, the carbonitride metal is selected from iron carbonitride, nickel carbonitride, cobalt carbonitride, or copper carbonitride.
[0049] In one embodiment of the present invention, the anode of the aluminum-ion battery is an aluminum electrode or an aluminum alloy electrode. The aluminum alloy contains silicon, with a silicon content of 0.1wt%-4wt%, which can improve the speed of aluminum power generation and charging and is beneficial to accelerating the aluminum reaction.
[0050] There are no particular limitations on the shape of the cathode or anode of the present invention, as long as the effect of the present invention can be achieved.
[0051] In one embodiment of the present invention, the electrolyte of the aluminum-ion battery comprises a eutectic solvent system of aluminum chloride and organic components, wherein the organic components include urea and / or triethylamine hydrochloride, and the molar ratio of aluminum chloride to organic components is 1:0.5-1. When the electrolyte comprises aluminum chloride and organic components, the electrolyte is in a eutectic solvent state during use.
[0052] In one embodiment of the present invention, the electrolyte comprises aluminum chloride and triethylamine hydrochloride, wherein the molar ratio of aluminum chloride to triethylamine hydrochloride is from 1.35:1 to 2.0:1. Typical but non-limiting molar ratios of aluminum chloride to triethylamine hydrochloride in the present invention are 1.35:1, 1.40:1, 1.45:1, 1.50:1, 1.55:1, 1.60:1, 1.65:1, 1.70:1, 1.75:1, 1.80:1, 1.85:1, 1.90:1, 1.95:1, or 2.0:1.
[0053] In one embodiment of the present invention, the electrolyte comprises aluminum chloride and urea, wherein the molar ratio of aluminum chloride to urea is from 1.35:1 to 2.0:1. Typical but non-limiting molar ratios of aluminum chloride to urea in the present invention are 1.35:1, 1.40:1, 1.45:1, 1.50:1, 1.55:1, 1.60:1, 1.65:1, 1.70:1, 1.75:1, 1.80:1, 1.85:1, 1.90:1, 1.95:1, or 2.0:1.
[0054] The melting point of the low cosolvent electrolyte system selected in this invention is between -10°C and 100°C, which can achieve discharge and charge at room temperature.
[0055] In one embodiment of the present invention, the electrolyte of the aluminum-ion battery comprises a molten salt system of aluminum chloride and chloride. When the electrolyte comprises aluminum chloride and chloride, the electrolyte is in a molten state during use. The chloride is at least one of lithium chloride, potassium chloride, and sodium chloride. The aluminum chloride content in the electrolyte is 40wt%-85wt%. Typical but non-limiting aluminum chloride contents in the present invention are 40wt%, 41wt%, 42wt%, 45wt%, 48wt%, 50wt%, 51wt%, 55wt%, 57wt%, 60wt%, 62wt%, 63wt%, 65wt%, 68wt%, 70wt%, 73wt%, 74wt%, 76wt%, 78wt%, 80wt%, 81wt%, 82wt%, 83wt%, 84wt%, or 85wt%.
[0056] In one embodiment of the present invention, the electrolyte includes aluminum chloride, sodium chloride and potassium chloride, wherein the sodium chloride content is 8wt%-40wt% and the potassium chloride content is 3wt%-20wt%.
[0057] In one embodiment of the present invention, the electrolyte includes aluminum chloride, sodium chloride and potassium chloride, and the mass ratio of aluminum chloride, sodium chloride and potassium chloride is 61:26:13.
[0058] In one embodiment of the present invention, the electrolyte comprises aluminum chloride, sodium chloride and potassium chloride, wherein the mass ratio of aluminum chloride, sodium chloride and potassium chloride is 57:29:14.
[0059] In one embodiment of the present invention, the electrolyte comprises aluminum chloride, sodium chloride and potassium chloride, wherein the mass ratio of aluminum chloride, sodium chloride and potassium chloride is 49:34:17.
[0060] In one embodiment of the present invention, the electrolyte contains 40wt%-85wt% aluminum chloride, 3wt%-20wt% potassium chloride, and 0-15wt% lithium chloride.
[0061] In one embodiment of the present invention, the electrolyte aluminum chloride content is 40wt%-85wt%, sodium chloride content is 8wt%-40wt%, potassium chloride content is 3wt%-20wt%, and lithium chloride content is 0-15wt%.
[0062] In one embodiment of the present invention, the electrolyte includes aluminum chloride, lithium chloride, potassium chloride and sodium chloride, wherein the mass ratio of aluminum chloride:sodium chloride:potassium chloride:lithium chloride is 75.77:11.7:4.76:7.77.
[0063] In one embodiment of the present invention, the electrolyte includes aluminum chloride, lithium chloride, potassium chloride and sodium chloride, wherein the mass ratio of aluminum chloride:sodium chloride:potassium chloride:lithium chloride is 77.67:11.36:7.08:3.88.
[0064] In one embodiment of the present invention, the electrolyte includes aluminum chloride, lithium chloride, potassium chloride and sodium chloride, wherein the mass ratio of aluminum chloride:sodium chloride:potassium chloride:lithium chloride is 76:11.7:7.3:5.0.
[0065] In one embodiment of the present invention, the electrolyte includes aluminum chloride, lithium chloride, potassium chloride and sodium chloride, wherein the mass ratio of aluminum chloride:sodium chloride:potassium chloride:lithium chloride is 72.69:11.22:4.57:11.51.
[0066] In one embodiment of the present invention, the electrolyte includes aluminum chloride, lithium chloride, potassium chloride and sodium chloride, wherein the mass ratio of aluminum chloride:sodium chloride:potassium chloride:lithium chloride is 71.02:10.93:6.82:11.21.
[0067] In one embodiment of the present invention, the electrolyte includes aluminum chloride, lithium chloride, potassium chloride and sodium chloride, wherein the mass ratio of aluminum chloride:sodium chloride:potassium chloride:lithium chloride is 72.07:10.54:6.57:10.81.
[0068] In one embodiment of the present invention, the electrolyte includes aluminum chloride, lithium chloride, potassium chloride and sodium chloride, wherein the mass ratio of aluminum chloride:sodium chloride:potassium chloride:lithium chloride is 53.27:27.10:10.28:9.34.
[0069] In one embodiment of the present invention, the electrolyte includes aluminum chloride, lithium chloride, potassium chloride and sodium chloride, wherein the mass ratio of aluminum chloride:sodium chloride:potassium chloride:lithium chloride is 76:5:7.3:11.7.
[0070] In one embodiment of the present invention, the electrolyte includes aluminum chloride, lithium chloride, potassium chloride and sodium chloride, wherein the mass ratio of aluminum chloride:sodium chloride:potassium chloride:lithium chloride is 82.2:3.8:5.3:8.6.
[0071] The melting point of the molten salt electrolyte provided in this embodiment of the invention is 55℃-250℃, preferably 55℃-176℃. Therefore, the working temperature range of the aluminum ion battery provided by this invention is 55℃-250℃, preferably 55℃-176℃, which belongs to the medium and low temperature aluminum ion battery category.
[0072] In this invention, the combination of the cathode material and the low-temperature molten salt electrolyte can reduce the operating temperature of the aluminum-ion battery from 130°C-250°C to 55-176°C, thereby reducing the viscosity coefficient of the electrolyte and improving its conductivity and ion mobility.
[0073] In this invention, aluminum chloride and the above-mentioned organic components are stirred at room temperature and mixed evenly to obtain a eutectic solvent electrolyte. Aluminum chloride and the above-mentioned chloride are then mixed and heated to a molten state to obtain a molten electrolyte.
[0074] In one embodiment of the present invention, the aluminum-ion battery further includes a separator for isolating the anode and cathode, the separator preventing the anode and cathode from contacting each other. In the present invention, the separator is made of a porous insulating material; more preferably, the insulating material includes lithium aluminate, glass, or ceramic.
[0075] In one embodiment of the present invention, the diaphragm is a porous ceramic, a porous glass, a glass fiber, or an aluminosilicate fiber, without particular limitation.
[0076] The aluminum-ion battery provided in this embodiment of the invention is a secondary battery. The cathode and anode are connected to the negative and positive terminals of an external power source, respectively, for charging. After charging is completed, the cathode and anode are connected to the negative and positive terminals of a load, respectively, for discharging. The battery can be recharged after discharging and reused.
[0077] In one embodiment of the present invention, a cylindrical aluminum-ion battery device is provided, such as... Figure 1As shown, the aluminum-ion battery includes an anode 1, a cathode 2, and an electrolyte 3 disposed between the anode 1 and the cathode 2. It also includes a cylindrical outer casing 4. The anode 1 is disposed in the center of a cavity formed within the casing 4. The cathode 2 is coated on or attached to the inner wall of the casing 4. The electrolyte 3 fills the cavity of the casing 4. In this embodiment, the aluminum-ion battery device further includes a separator 5, which is disposed between the anode 1 and the cathode 2 to isolate the contact between the anode 1 and the cathode 2. In some embodiments, the separator 5 may be disposed close to the cathode 2.
[0078] In one embodiment of the present invention, the anode and cathode are immersed in an electrolyte, and a separator is placed between the anode and cathode to assemble an aluminum-ion battery.
[0079] Example 1: Ferric oxide cathode + aluminum chloride + triethylamine hydrochloride eutectic solvent aluminum-ion battery
[0080] The eutectic solvent electrolyte is prepared at room temperature by mixing 7.8g of anhydrous aluminum chloride and 5.34g of triethylamine hydrochloride and stirring to melt it at room temperature. The operation must be carried out at a dew point temperature of -40 degrees Celsius and humidity, and strictly isolated from moisture in the air. The pH value is less than -1. The conductivity is about 7ms / cm at 23℃. After drying in an oven at 85℃, the conductivity is 17ms / cm at 60-70℃ and 9ms / cm at 43℃.
[0081] The negative electrode of the aluminum-ion battery is an aluminum sheet with a diameter of 30 mm and a thickness of 600 micrometers; the electrolyte is a eutectic solvent; the cathode is 10 wt% ferric oxide + 90 wt% graphite, pressed into a membrane with a thickness of 2 mm; the separator is a glass fiber separator, assembled into a battery.
[0082] Using a power supply tester, the battery's open-circuit voltage was measured to be 0.769 volts and its short-circuit current to be 49 milliamperes.
[0083] The specific capacity of the battery was determined to be 70 mAh / g using the Chenhua electrochemical workstation.
[0084] Example 2: Manganese dioxide cathode + aluminum chloride urea eutectic solvent aluminum ion battery
[0085] Prepare a eutectic solvent electrolyte at room temperature: Take 20 grams of aluminum chloride and 6 grams of urea, stir and melt to obtain a clear liquid, and measure the conductivity at room temperature as 5 mS / cm.
[0086] The negative electrode of the aluminum-ion battery is an aluminum sheet, the electrolyte is a prepared aluminum chloride urea eutectic solvent, the cathode is manganese dioxide coated on a graphite electrode, and the separator is a glass fiber separator, which is assembled into a battery.
[0087] Using a power supply tester, the battery's open-circuit voltage was measured to be 1.5 volts, its internal resistance to be 0.8 ohms, its short-circuit current to be 42 mA, and its average discharge voltage to be 1.0 volts.
[0088] Example 3: Manganese dioxide cathode molten salt aluminum ion battery
[0089] Preparation of molten salt electrolyte: Weigh 76g of aluminum chloride, 11.7g of sodium chloride, 7.3g of potassium chloride, and 5g of lithium chloride. Mix thoroughly and heat to 100℃ to melt, obtaining a quaternary molten salt electrolyte. The freezing point is 75℃. At 80℃, the conductivity of the molten salt is 83 mS / cm.
[0090] Aluminum-ion battery: Aluminum sheet as negative electrode, glass fiber separator, manganese dioxide coated on graphite electrode as positive electrode, and quaternary molten salt electrolyte are used to prepare the battery. Using a power supply tester, the battery's open-circuit voltage is 1.7 volts, internal resistance is 0.3 ohms, and short-circuit current is 400 mA.
[0091] Example 4: Graphite cathode, aluminum chloride, triethylamine hydrochloride, eutectic solvent, aluminum-ion battery
[0092] Preparation of eutectic solvent electrolyte: Take 10 g of aluminum chloride and 6.7 g of triethylamine hydrochloride, stir and melt to obtain a clear liquid, and measure the conductivity at room temperature to be 12 mS / cm.
[0093] Battery: The negative electrode is an aluminum-silicon alloy sheet with a silicon content of 4wt%, the separator is a glass fiber separator, the positive electrode is a flake graphite electrode, and a eutectic solvent electrolyte is configured to assemble the battery.
[0094] Using a power supply tester, the battery's open-circuit voltage was measured to be 1.6 volts, indicating that the battery can undergo charge-discharge testing. Figure 2 As shown, the discharge specific capacity is 49mAh / g, indicating that the aluminum-ion battery in this embodiment can be charged and discharged normally, achieving charge-discharge cycle.
[0095] like Figure 3 As shown, the discharge specific capacity reaches 180 mAh / g, and at 2.5C, the discharge specific capacity is 80-90 mAh / g. This indicates that the battery possesses high energy density. It also demonstrates that this invention achieves high discharge specific capacity through the combination of a graphite cathode, electrolyte, and aluminum anode.
[0096] like Figure 4 As shown, the charge and discharge efficiency of aluminum-ion batteries can be stably maintained between 95% and 98%, far exceeding the power generation efficiency of aluminum-air batteries in aqueous solutions, which is 15% to 30%.
[0097] Example 5: Graphite Cathode Molten Salt Aluminum Ion Battery
[0098] Molten salt electrolyte preparation: Weigh 10g of aluminum chloride, 1.05g of sodium chloride, 0.65g of potassium chloride, and 0.46g of lithium chloride, mix thoroughly, and heat to 120℃ to melt. At 120℃, the conductivity of the molten salt is 75 mS / cm.
[0099] Aluminum-ion battery: Aluminum negative electrode sheet, glass fiber separator, expanded graphite positive electrode, and quaternary molten salt electrolyte are assembled into a battery.
[0100] The battery open-circuit voltage was measured to be 1.4 volts using a power supply tester.
[0101] The battery undergoes charge and discharge testing, such as Figure 5 As shown, the discharge specific capacity is 22 mAh / g.
[0102] like Figure 5 It can be seen that the battery can be charged and discharged, realizing reversible charging and discharging, and has the function of an energy storage battery.
[0103] Example 6: Ferrous oxide cathode, aluminum chloride, triethylamine hydrochloride, eutectic solvent, aluminum-ion battery
[0104] Preparation of eutectic solvent electrolyte: Take 10 g of aluminum chloride and 6.7 g of triethylamine hydrochloride, stir and melt to obtain a clear liquid, and measure the conductivity at room temperature to be 12 mS / cm.
[0105] Battery: Aluminum sheet for negative electrode, glass fiber separator for separator, 10wt% to 70wt% ferrous oxide for positive electrode, the remainder being graphite conductive agent, and electrolyte prepared with eutectic solvent, assembled into a battery.
[0106] The battery underwent charge and discharge testing. Figure 6 The charge-discharge curves of different ferrous oxide contents are shown. The cathode materials with 10% to 20% ferrous oxide contents have a specific capacity of 90 mAh / g, which is relatively high.
[0107] Figure 7 The discharge specific capacity of a cathode containing 30 wt% ferrous oxide at different rates was shown, and cyclic charge-discharge was achieved from 0.6C to 30C, with a discharge specific capacity of 30-90 mA / g.
[0108] Throughout this specification, references to "an example," "an embodiment," or "an embodiment" indicate that a particular feature, structure, or characteristic described in connection with an embodiment is included in at least one embodiment. Therefore, the appearance of "an example," "an embodiment," or "an embodiment" in various places throughout this specification does not necessarily refer to the same embodiment. Furthermore, a particular feature, structure, or characteristic may be combined in any manner in one or more embodiments.
[0109] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.
Claims
1. A cathode for an aluminum-ion battery, characterized in that, The cathode contains an active material, which is manganese dioxide, ferric oxide, ferrous oxide, iron oxide, copper oxide, graphite, or metal carbonitride, wherein the metal element includes at least one selected from gold, silver, copper, platinum, palladium, iron, cobalt, and nickel.
2. The cathode of the aluminum-ion battery according to claim 1, characterized in that, The metal element content in the graphite loaded with metal elements or the carbonitride is 1wt%-30wt%.
3. The cathode of the aluminum-ion battery according to claim 1 or 2, characterized in that, When the active material of the cathode is manganese dioxide, ferric oxide, ferrous oxide, magnetite, copper oxide, or metal carbonitride, the cathode also contains a conductive agent. Preferably, the conductive agent accounts for 20wt-50wt% of the mass of the active material.
4. The cathode of the aluminum-ion battery according to claim 1 or 2, characterized in that, When the active material of the cathode is manganese dioxide, ferric oxide, ferrous oxide, iron(II) oxide, copper oxide, or metal carbonitride, the active material is prepared into a slurry and coated onto a graphite electrode to form a cathode.
5. An aluminum-ion battery, characterized in that, The cathode of the aluminum ion battery is the cathode described in any one of claims 1-4.
6. The aluminum-ion battery according to claim 5, characterized in that, The aluminum-ion battery further includes an anode, the anode being made of aluminum or an aluminum alloy, wherein the aluminum alloy contains silicon. Preferably, the silicon content in the aluminum alloy is 0.1 wt% to 4.0 wt% by mass.
7. The aluminum-ion battery according to claim 5 or 6, characterized in that, The aluminum-ion battery also includes an electrolyte, which comprises a eutectic solvent system of aluminum chloride and organic components, wherein the organic components include urea and / or triethylamine hydrochloride, and the molar ratio of aluminum chloride to organic components is 1:0.5-1.
8. The aluminum-ion battery according to claim 7, characterized in that, The electrolyte comprises aluminum chloride and triethylamine hydrochloride, wherein the molar ratio of aluminum chloride to triethylamine hydrochloride is 1.35:1 to 2.0:
1.
9. The aluminum-ion battery according to claim 7, characterized in that, The electrolyte comprises aluminum chloride and urea, wherein the molar ratio of aluminum chloride to urea is 1.35:1 to 2.0:
1.
10. The aluminum-ion battery according to claim 5 or 6, characterized in that, The aluminum-ion battery also includes an electrolyte, which comprises a molten salt system of aluminum chloride and chloride, wherein the chloride is at least one of lithium chloride, potassium chloride, and sodium chloride, and the mass percentage of aluminum chloride in the electrolyte is 40wt%-85wt%.
11. The aluminum-ion battery according to claim 10, characterized in that, The electrolyte includes aluminum chloride, sodium chloride and potassium chloride, with sodium chloride content of 8wt%-40wt% and potassium chloride content of 3wt%-20wt%.
12. The aluminum-ion battery according to claim 10, characterized in that, The electrolyte contains 40wt%-85wt% aluminum chloride, 3wt%-20wt% potassium chloride, and 0-15wt% lithium chloride.
13. The aluminum-ion battery according to claim 10, characterized in that, The electrolyte contains 40wt%-85wt% aluminum chloride, 8wt%-40% sodium chloride, 3-20% potassium chloride, and 0-15% lithium chloride.
14. A cylindrical aluminum-ion battery device, comprising the aluminum-ion battery according to any one of claims 5-13, wherein the aluminum-ion battery comprises an anode, a cathode, and an electrolyte disposed between the anode and the cathode; The cylindrical aluminum-ion battery device also includes a cylindrical outer shell, the anode is disposed in the center of a cavity formed inside the outer shell, the cathode is coated on or attached to the inner wall of the outer shell, and the electrolyte is filled in the cavity of the outer shell. Preferably, the aluminum-ion battery further includes a separator disposed between the aluminum anode and the air cathode. Preferably, the diaphragm is disposed close to the air cathode.