Aqueous Hydrogen-Chlorine Dual-Ion Rechargeable Battery and Its Preparation Method

Abstract

This invention discloses an aqueous hydrogen-chlorine dual-ion rechargeable battery and its preparation method. The aqueous hydrogen-chlorine dual-ion rechargeable battery includes a positive electrode, a negative electrode, and an electrolyte. The active material of the positive electrode is an aluminate oxide with the chemical formula MAl₂O₄, wherein M is at least one of Cu, Mg, and Zn. The electrolyte is an acidic aqueous solution containing hydrogen and chloride ions. This aqueous hydrogen-chlorine dual-ion rechargeable battery, through the combined action of hydrogen and chloride ions and its combination with the aluminate oxide positive electrode material, not only improves the battery's capacity but also enhances its overall structural stability, resulting in better cycle performance. It possesses advantages such as high specific capacity, excellent cycle performance, and superior rate performance, making it a promising energy storage device.

Description

Technical Field

[0001] This invention belongs to the field of aqueous battery technology, specifically relating to an aqueous hydrogen-chlorine dual-ion rechargeable battery and its preparation method. Background Technology

[0002] Over the past few decades, these technological advancements in lithium-ion batteries have had a dramatic and profound impact on society. The widespread use of lithium-ion batteries has essentially laid the foundation for ubiquitous portable electronics and has also made a fossil fuel-free society possible, powered by renewable energy. However, commercially available lithium-ion batteries have almost reached their limits, not only in terms of energy density (~200 Wh / kg) -1 Furthermore, this is also true in terms of cycle life (1000 cycles, >80%) and rate capability (1C). Uneven distribution and soaring prices of lithium sources also make large-scale lithium-ion battery applications difficult and costly. In addition, safety issues related to lithium dendrites, especially at high rates, are another obstacle to developing high-energy-density lithium-ion batteries with superior performance.

[0003] Compared to metal ions, the lightest and smallest non-metallic protons, as charge carriers, exhibit faster kinetics and higher energy density. Acidic solutions are typically the default proton donor. Currently, hydrogen-ion batteries primarily use H₂SO₄ as the electrolyte to ionize H₂, but H₂ is easily attracted by the solvent H₂O, with a desolvation energy as high as 11.66 eV. Therefore, in acidic solutions, H₂ still primarily functions as a proton donor in H₃O₄. + It exists in the form of H. Compared to H, H3O + The larger ionic radius limits the choice of electrode materials. It is worth noting that H3O + Acting as a charge carrier does not alter the nature of the bond between hydrogen and oxygen. High concentrations of weak acids such as H₃PO₄ are also considered proton donors. Furthermore, the presence of H is often negligible in mild electrolytes. According to the Brónsted-Lowry acid-base theory, polyvalent metal ions, such as Zn₂… 2+ And Al 3+ It can react with H2O solvent to form a conjugate base and produce H.

[0004] Compared to Li + Zn 2+ And Al 3+Isocational batteries, anion batteries, and anion / cation dual-ion batteries are another hot topic, offering the possibility of designing high-energy-density batteries by selecting appropriate electrochemical couplings. Recent research has frequently highlighted chloride-ion batteries, a key advantage of which utilizes chloride-containing electrolytes, which can be abundant in natural forms, such as NaCl solution (i.e., seawater). In this pioneering work, metal chlorides and metal oxychlorides were selected as potential cathode materials, while lithium or magnesium were considered for the anode. Electrolytes are typically chloride-containing compounds dissolved in ionic liquids or organic solvents, but these are often hazardous methods. However, achieving chloride ion shuttle in aqueous electrolytes remains a significant challenge due to the instability or high solubility of most electrode materials in such solutions; moreover, these materials suffer from low capacity, poor cycle stability, and poor rate performance, leaving considerable room for improvement before commercialization. Therefore, overcoming these difficulties and finding an aqueous battery with high specific capacity, excellent cycle performance, and superior rate performance has become a research hotspot and key issue in battery development. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide an aqueous hydrogen-chlorine dual-ion rechargeable battery with high specific capacity, excellent cycle performance and rate performance, and a method for preparing the same.

[0006] To solve the above-mentioned technical problems, the present invention adopts the following technical solution.

[0007] An aqueous hydrogen-chlorine dual-ion rechargeable battery includes a positive electrode, a negative electrode, and an electrolyte. The active material of the positive electrode is an aluminate oxide with the chemical formula MAl2O4, wherein M is at least one of Cu, Mg, and Zn. The electrolyte is an acidic aqueous solution containing hydrogen ions and chloride ions.

[0008] In a further improvement of the aforementioned aqueous hydrogen-chlorine dual-ion rechargeable battery, the acidic aqueous solution containing hydrogen and chloride ions is prepared from chloride, acidic solution, and water; the concentration of chloride in the acidic aqueous solution containing hydrogen and chloride ions is 0.5 mol / L to 4 mol / L, and the pH value of the acidic aqueous solution containing hydrogen and chloride ions is 1 to 6.

[0009] In a further improvement of the aforementioned aqueous hydrogen-chlorine dual-ion rechargeable battery, the chloride is at least one of a metal chloride and tetramethylammonium chloride, and the metal chloride is at least one of aluminum chloride, magnesium chloride, zinc chloride, copper chloride, manganese chloride, nickel chloride, ferric chloride, lithium chloride, sodium chloride, and potassium chloride; the volume of the acidic solution accounts for 1% to 10% of the total volume of the acidic aqueous solution containing hydrogen ions and chloride ions, the concentration of the acidic solution is 0.1 mol / L to 1 mol / L, and the acidic solution is at least one of acetic acid aqueous solution, hydrochloric acid solution, phosphoric acid solution, carbonic acid solution, and sulfuric acid solution.

[0010] A further improvement to the above-mentioned aqueous hydrogen-chlorine dual-ion rechargeable battery is the preparation method of the aluminate oxide, which includes the following steps:

[0011] (1) Aluminum salt, metal M salt and water are mixed to obtain a mixed solution; wherein the metal M salt is at least one of copper salt, magnesium salt and zinc salt;

[0012] (2) Mix the mixed solution obtained in step (1) with the precipitant, adjust the pH value to 6.5-12, carry out the reaction, age, wash and dry to obtain the precursor;

[0013] (3) The precursor obtained in step (2) is sintered to obtain aluminate oxide.

[0014] In a further improvement of the above-mentioned aqueous hydrogen-chlorine dual-ion rechargeable battery, the total molar concentration of aluminum ions and M ions in the mixed solution is 0.1 mol / L to 4 mol / L, the molar ratio of the aluminum salt to the metal M salt is 1:1, and the molar ratio of the precipitant to the total molar amount of aluminum ions and M ions in the mixed solution is 4 to 8:1.

[0015] In a further improvement of the aforementioned aqueous hydrogen-chlorine dual-ion rechargeable battery, the aluminum salt is at least one of aluminum nitrate, aluminum chloride, aluminum sulfate, and aluminum trifluoromethanesulfonate; the copper salt is at least one of copper sulfate, copper chloride, copper sulfamate, copper bromide, copper nitrate, and copper acetate; the magnesium salt is at least one of magnesium sulfate, magnesium chloride, magnesium sulfamate, magnesium bromide, magnesium nitrate, and magnesium acetate; the zinc salt is at least one of zinc sulfate, zinc chloride, zinc sulfamate, zinc bromide, zinc nitrate, and zinc acetate; and the precipitant is at least one of ammonium bicarbonate, ammonium carbonate, urea, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, oxalic acid, sodium hydroxide, and potassium hydroxide.

[0016] In a further improvement of the above-mentioned aqueous hydrogen-chlorine dual-ion rechargeable battery, in step (1), the mixing is carried out under stirring conditions, the stirring speed is 200 rpm to 2000 rpm, and the mixing temperature is 20°C to 80°C.

[0017] And / or, in step (2), the reaction time is 10 min to 60 min, the aging time is 6 h to 24 h, the drying temperature is 60 ° C to 120 ° C, and the drying time is 2 h to 12 h;

[0018] And / or, in step (3), the sintering temperature is 700℃~1600℃, the sintering time is 2h~96h, and the heating rate during the sintering process is 1℃ / min~15℃ / min.

[0019] In a further improvement of the aforementioned aqueous hydrogen-chlorine dual-ion rechargeable battery, the negative electrode material is any one of aluminum, magnesium, zinc, copper, nickel, iron, manganese, silver, lead, and carbon materials, and the carbon material is any one of graphite, activated carbon, hard carbon, soft carbon, and graphene. The negative electrode material is in the form of foil or powder. The aqueous hydrogen-chlorine dual-ion rechargeable battery also includes a separator.

[0020] As a general technical concept, the present invention also provides a method for preparing the above-mentioned aqueous hydrogen-chlorine dual-ion rechargeable battery, comprising the following steps:

[0021] S1. Aluminate oxide, conductive agent, binder and solvent are mixed to form slurry A. Slurry A is coated on the positive electrode current collector and then rolled and dried to form the positive electrode.

[0022] S2. Mix the negative electrode material, conductive agent and binder to form slurry B, coat slurry B onto the current collector and dry it to form the negative electrode; or, use foil directly as the negative electrode.

[0023] S3. Assemble the positive electrode obtained in step S1, the negative electrode obtained in step S2, the electrolyte, and the separator to obtain an aqueous hydrogen-chlorine dual-ion rechargeable battery; the electrolyte is an acidic aqueous solution containing hydrogen ions and chloride ions.

[0024] In a further improvement to the above preparation method, in step S1, the mass ratio of the aluminate oxide, conductive agent, and binder is 70-94:15-3:15-3, and the positive electrode current collector is any one of copper foil, copper mesh, titanium foil, titanium mesh, molybdenum foil, and carbon paper.

[0025] In step S2, the mass of the conductive agent accounts for 2% to 10% of the total mass of slurry B, and the mass of the binder accounts for 2% to 10% of the total mass of slurry B.

[0026] Compared with the prior art, the advantages of the present invention are as follows:

[0027] (1) This invention provides an aqueous hydrogen-chlorine dual-ion rechargeable battery. The active material of the positive electrode is aluminate oxide (chemical formula MAl2O4), and the electrolyte is an acidic aqueous solution containing hydrogen and chloride ions. Compared with the defects of hydrogen-ion batteries and chloride-ion batteries, namely, whether it is single chloride ion insertion or hydrogen ion energy storage, the capacity of hydrogen-ion batteries and chloride-ion batteries is not very high, and the stability needs to be improved. The aqueous hydrogen-chlorine dual-ion rechargeable battery of this invention, through the combined action of hydrogen and chloride ions and the combination with aluminate oxide positive electrode material, can not only improve the battery capacity, but also improve the overall structural stability of the battery, so that the battery has better cycle performance. The aqueous hydrogen-chlorine dual-ion rechargeable battery of this invention has a working voltage plateau of 1.63V at a current density of 300mA / g, an initial discharge capacity of 81.6mAh / g, and a discharge capacity of 105.5mAh / g after 50 cycles. The aqueous hydrogen-chlorine dual-ion rechargeable battery of the present invention has advantages such as high specific capacity, excellent cycle performance and rate performance, and is a promising energy storage device.

[0028] (2) This invention also provides a method for preparing aluminate oxides, wherein a precursor is prepared by co-precipitation and then sintered to obtain the aluminate oxides. The aluminate oxides used in this invention have an Fd-3m structure, which is more stable and, when used as the positive electrode material of an aqueous hydrogen-chlorine dual-ion rechargeable battery, is more conducive to the transfer and intercalation of hydrogen and chloride ions, thus possessing better cycle performance. The preparation method of this invention has the advantages of simple process, low cost and environmental friendliness, and is suitable for large-scale industrial production; the aluminate oxides obtained therefrom, as the positive electrode material of an aqueous hydrogen-chlorine dual-ion rechargeable battery, have the advantages of stable structure, excellent performance, high specific capacity, and excellent cycle performance and rate performance. Attached Figure Description

[0029] Figure 1 This is a cycle performance diagram of the aqueous hydrogen-chlorine dual-ion rechargeable battery in Embodiment 1 of the present invention.

[0030] Figure 2 This is a cycle performance diagram of the aqueous hydrogen-chlorine dual-ion rechargeable battery in Embodiment 2 of the present invention.

[0031] Figure 3 This is a cycle performance diagram of the aqueous hydrogen-chlorine dual-ion rechargeable battery in Embodiment 3 of the present invention.

[0032] Figure 4 This is a cycle performance diagram of the aqueous hydrogen-chlorine dual-ion rechargeable battery in Example 4 of the present invention.

[0033] Figure 5 The image shows the XRD pattern of the aluminate oxide ZnAl2O4 prepared in Example 5 of this invention.

[0034] Figure 6 This is a cycle performance diagram of the aqueous hydrogen-chlorine dual-ion rechargeable battery in Embodiment 5 of the present invention.

[0035] Figure 7 The graph shows the cycle performance of the aqueous chloride-ion battery in Comparative Example 1.

[0036] Figure 8 The graph shows the cycle performance of the aqueous hydrogen-ion battery in Comparative Example 2. Detailed Implementation

[0037] The present invention will be further described below with reference to the accompanying drawings and specific preferred embodiments, but this does not limit the scope of protection of the present invention. All materials and instruments used in the following embodiments are commercially available.

[0038] Example 1:

[0039] A water-based hydrogen-chlorine dual-ion rechargeable battery of the present invention includes a positive electrode, a negative electrode, and an electrolyte. The active material of the positive electrode is aluminate oxide CuAl2O4. The electrolyte is an acidic aqueous solution containing hydrogen and chloride ions, which is composed of aluminum chloride, an acidic solution, and water. The concentration of aluminum chloride in the electrolyte is 4 mol / L, the pH value of the electrolyte is 1, the acidic solution is a hydrochloric acid solution with a concentration of 1 mol / L, and the volume of the hydrochloric acid solution accounts for 3% of the total volume of the electrolyte.

[0040] In this embodiment, the preparation method of the aluminate oxide CuAl2O4 includes the following steps:

[0041] (1) Disperse aluminum sulfate and copper sulfate in deionized water and mechanically stir at 500 rpm and 25°C to obtain a mixed solution; wherein the molar ratio of aluminum sulfate and copper sulfate is 1:1 and the total molar concentration of aluminum ions and copper ions in the precursor solution is 1 mol / L.

[0042] (2) Mix the mixed solution from step (1) with ammonium bicarbonate, add ammonia to adjust the pH to 9, react for 60 min, and let stand for 24 h; then, filter the solution after standing and aging using a Buchner funnel, and dry it in an 80℃ vacuum drying oven for 24 h to obtain the precursor powder; wherein, the molar ratio of ammonium bicarbonate to the total molar amount of aluminum ions and copper ions in the precursor solution is 5:1.

[0043] (3) After mechanically grinding the precursor powder obtained in step (2) evenly, place it in a high-temperature sintering furnace, heat it to 1100℃ at a heating rate of 5℃ / min, keep it at that temperature for 96 hours, cool it and then crush it for 5 minutes, pass it through a 300-mesh sieve, and demagnetize it with a demagnetizer to obtain aluminate oxide CuAl2O4.

[0044] The aluminate oxide CuAl2O4, super carbon black, polyvinylidene fluoride (PVDF), and N-methylpyrrolidone (NMP) prepared by the above method were mixed evenly to form a slurry. This slurry was then uniformly coated onto titanium foil and vacuum dried at 120°C for 12 hours to obtain the positive electrode sheet. The coating surface density of the positive electrode sheet was 5 mg / cm³. 2 Electrochemical performance was tested using a three-electrode simulated battery. A platinum electrode was used as the counter electrode, and a silver / silver chloride electrode was used as the reference electrode. The electrolyte was an acidic aqueous solution containing hydrogen and chloride ions, as described above. Charge-discharge tests were conducted at room temperature at a current density of 100 mA / g, with a test voltage range of 0–1.2 V.

[0045] Figure 1 This is a cycle performance diagram of the aqueous hydrogen-chlorine dual-ion rechargeable battery in Embodiment 1 of the present invention. From... Figure 1 It can be seen that the initial discharge capacity of the aqueous hydrogen-chlorine dual-ion rechargeable battery is 120mAh / g, which increases to 150mAh / g after 50 cycles.

[0046] Example 2:

[0047] A water-based hydrogen-chlorine dual-ion rechargeable battery of the present invention includes a positive electrode, a negative electrode and an electrolyte. The active material of the positive electrode is aluminate oxide CuAl2O4. The electrolyte is an acidic aqueous solution containing hydrogen ions and chloride ions, and the electrolyte of Example 1 is used.

[0048] In this embodiment, the preparation method of aluminate oxide CuAl2O4 is basically the same as that of aluminate oxide CuAl2O4 in Example 1, except that in step (1), copper acetate is used instead of copper sulfate.

[0049] The aluminate oxide CuAl2O4, super carbon black, polyvinylidene fluoride (PVDF), and N-methylpyrrolidone (NMP) prepared by the above method were mixed evenly to form a slurry. This slurry was then uniformly coated onto titanium foil and vacuum dried at 120°C for 12 hours to obtain the positive electrode sheet. The coating surface density of the positive electrode sheet was 5 mg / cm³. 2 Electrochemical performance was tested using a three-electrode simulated battery. A platinum electrode was used as the counter electrode, and a silver / silver chloride electrode was used as the reference electrode. The electrolyte was an acidic aqueous solution containing hydrogen and chloride ions, as described above. Charge-discharge tests were conducted at room temperature at a current density of 100 mA / g, with a test voltage range of 0–1.2 V.

[0050] Figure 2This is a cycle performance diagram of the aqueous hydrogen-chlorine dual-ion rechargeable battery in Embodiment 2 of the present invention. From... Figure 1 It can be seen that the initial discharge capacity of the aqueous hydrogen-chlorine dual-ion rechargeable battery is 141 mAh / g, which increases to 209 mAh / g after 50 cycles.

[0051] Example 3:

[0052] A water-based hydrogen-chlorine dual-ion rechargeable battery of the present invention includes a positive electrode, a negative electrode, a separator, and an electrolyte. The active material of the positive electrode is aluminate oxide CuAl2O4; the active material of the negative electrode is metallic aluminum; the separator is a glass fiber separator; and the electrolyte is an acidic aqueous solution containing hydrogen ions and chloride ions, using the electrolyte of Example 1.

[0053] In this embodiment, the aluminate oxide CuAl2O4 used is the aluminate oxide CuAl2O4 obtained in Example 2.

[0054] The assembly of an aqueous hydrogen-chlorine dual-ion rechargeable battery according to this embodiment includes the following steps:

[0055] S1, Positive electrode

[0056] According to the mass ratio of aluminate oxide CuAl2O4, super carbon black, polyvinylidene fluoride (PVDF), and N-methylpyrrolidone (NMP) of 80:10:10:25, the aluminate oxide CuAl2O4, super carbon black, PVDF, and N-methylpyrrolidone prepared in Example 2 were mixed evenly to form slurry A, which was then uniformly coated on titanium foil and vacuum dried at 120°C for 12 hours. After rolling, the positive electrode was obtained, with a coating surface density of 5 mg / cm³. 2 In this step, super carbon black is used as a conductive agent, polyvinylidene fluoride as a binder, and N-methylpyrrolidone as a solvent.

[0057] S2, negative electrode

[0058] Aluminum powder, Ketjen black, and polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 90:5:5 to form a slurry. This slurry was then uniformly coated onto titanium foil and dried to obtain the negative electrode. In this step, Ketjen black served as a conductive agent, and PVDF served as a binder.

[0059] S3, Assembly

[0060] The positive electrode obtained in step S1, the negative electrode obtained in step S2, the electrolyte, and the glass fiber separator are assembled and encapsulated in an aluminum-plastic film shell to produce an aqueous hydrogen-chlorine dual-ion rechargeable battery. The electrolyte is the aforementioned acidic aqueous solution containing hydrogen and chloride ions.

[0061] Figure 3This is a cycle performance diagram of the aqueous hydrogen-chlorine dual-ion rechargeable battery in Example 3 of the present invention. Charge-discharge tests were conducted at room temperature with a current density of 300 mA / g and a voltage range of 0–2V. Figure 3 It can be seen that at a current density of 300 mA / g, the working voltage platform of the aqueous hydrogen-chlorine dual-ion rechargeable battery is 1.63V, the initial discharge capacity is 81.6mAh / g, and after 50 cycles, the discharge capacity is 105.5mAh / g.

[0062] Example 4:

[0063] A water-based hydrogen-chlorine dual-ion rechargeable battery of the present invention includes a positive electrode, a negative electrode and an electrolyte. The active material of the positive electrode is aluminate oxide MgAl2O4. The electrolyte is an acidic aqueous solution containing hydrogen ions and chloride ions, and the electrolyte of Example 1 is used.

[0064] In this embodiment, the preparation method of aluminate oxide MgAl2O4 includes the following steps:

[0065] (1) Disperse aluminum sulfate and magnesium sulfate in deionized water and mechanically stir at 500 rpm and 25°C to obtain a precursor solution; wherein the molar ratio of aluminum sulfate and magnesium sulfate is 1:1 and the total molar concentration of aluminum ions and magnesium ions in the precursor solution is 1 mol / L.

[0066] (2) Mix the precursor solution from step (1) with ammonium bicarbonate, add ammonia to adjust the pH to 9, react for 60 min, and let stand for 24 h; then, filter the solution after standing and aging using a Buchner funnel, and dry it in an 80℃ vacuum drying oven for 24 h to obtain precursor powder; wherein, the molar ratio of ammonium bicarbonate to the total molar amount of aluminum ions and magnesium ions in the precursor solution is 5:1.

[0067] (3) After mechanically grinding the precursor powder obtained in step (2) evenly, place it in a high-temperature sintering furnace, heat it to 1100℃ at a heating rate of 5℃ / min, keep it at the temperature for 12 hours, cool it and then crush it for 5 minutes, pass it through a 300-mesh sieve, and demagnetize it with a demagnetizer to obtain aluminate oxide MgAl2O4.

[0068] The aluminate oxide MgAl2O4, super carbon black, polyvinylidene fluoride (PVDF), and N-methylpyrrolidone (NMP) prepared by the above method were mixed evenly to form a slurry. This slurry was then uniformly coated onto titanium foil and vacuum dried at 120°C for 12 hours to obtain the positive electrode sheet. The coating surface density of the positive electrode sheet was 5 mg / cm³. 2Electrochemical performance was tested using a three-electrode simulated battery. A platinum electrode was used as the counter electrode, and a silver / silver chloride electrode was used as the reference electrode. The electrolyte was an acidic aqueous solution containing hydrogen and chloride ions, as described above. Charge-discharge tests were conducted at room temperature at a current density of 100 mA / g, with a test voltage range of 0–1.2 V.

[0069] Figure 4 This is a cycle performance diagram of the aqueous hydrogen-chlorine dual-ion rechargeable battery in Example 4 of the present invention. From... Figure 4 It can be seen that the initial discharge capacity of the aqueous hydrogen-chlorine dual-ion rechargeable battery is 218 mAh / g, which increases to 261 mAh / g after 50 cycles.

[0070] Example 5:

[0071] A water-based hydrogen-chlorine dual-ion rechargeable battery of the present invention includes a positive electrode, a negative electrode and an electrolyte. The active material of the positive electrode is aluminate oxide ZnAl2O4. The electrolyte is an acidic aqueous solution containing hydrogen ions and chloride ions, and the electrolyte of Example 1 is used.

[0072] In this embodiment, the preparation method of the aluminate oxide ZnAl2O4 includes the following steps:

[0073] (1) Disperse aluminum sulfate and zinc sulfate in deionized water and mechanically stir at 500 rpm and 25°C to obtain a precursor solution; wherein the molar ratio of aluminum sulfate and zinc sulfate is 1:1 and the total molar concentration of aluminum ions and zinc ions in the precursor solution is 1 mol / L.

[0074] (2) Mix the precursor solution from step (1) with ammonium bicarbonate, add ammonia to adjust the pH to 9, react for 50 min, and let stand for 24 h; then, filter the solution after standing and aging using a Buchner funnel, and dry it in an 80℃ vacuum drying oven for 24 h to obtain precursor powder; wherein, the molar ratio of ammonium bicarbonate to the total molar amount of aluminum ions and zinc ions in the precursor solution is 5:1.

[0075] (3) After mechanically grinding the precursor powder obtained in step (2) evenly, place it in a high-temperature sintering furnace, heat it to 700°C at a heating rate of 5°C / min, keep it at that temperature for 12 hours, cool it and then crush it for 5 minutes, pass it through a 300-mesh sieve, and demagnetize it with a demagnetizer to obtain aluminate oxide ZnAl2O4.

[0076] Figure 5 The image shows the XRD pattern of the aluminate oxide ZnAl2O4 obtained in Example 5 of this invention. According to the standard PDF card, the synthesized ZnAl2O4 is a pure phase without impurities, has an Fd-3m structure, is structurally stable, can withstand higher current densities, and exhibits better cycling performance.

[0077] The aluminate oxide ZnAl2O4, super carbon black, polyvinylidene fluoride (PVDF), and N-methylpyrrolidone (NMP) were mixed evenly according to a mass ratio of 80:10:10:25 to form a slurry. This slurry was then uniformly coated onto titanium foil and vacuum dried at 120°C for 12 hours to obtain a positive electrode sheet with a coating surface density of 5 mg / cm³. 2 Electrochemical performance was tested using a three-electrode simulated battery. A platinum electrode was used as the counter electrode, and a silver / silver chloride electrode was used as the reference electrode. The electrolyte was an acidic aqueous solution containing hydrogen and chloride ions, as described above. Charge-discharge tests were conducted at room temperature at a current density of 100 mA / g, with a test voltage range of 0–1.2 V.

[0078] Figure 6 This is a cycle performance diagram of the aqueous hydrogen-chlorine dual-ion rechargeable battery in Embodiment 5 of the present invention. From... Figure 5 It can be seen that the initial discharge capacity of the aqueous hydrogen-chlorine dual-ion rechargeable battery is 143 mAh / g, which increases to 154 mAh / g after 50 cycles.

[0079] Comparative Example 1:

[0080] An aqueous chloride-ion battery includes a positive electrode, a negative electrode, and an electrolyte. The active material of the positive electrode is aluminate oxide ZnAl2O4. The electrolyte is an aqueous solution of sodium chloride with a neutral pH.

[0081] In Comparative Example 1, the aluminate oxide ZnAl2O4 used was the aluminate oxide ZnAl2O4 prepared in Example 5.

[0082] Electrochemical performance was tested using a three-electrode simulated battery. The positive electrode was the same as that in Example 5, the counter electrode was a platinum electrode, and the reference electrode was a silver / silver chloride electrode. The electrolyte was the acidic aqueous solution containing hydrogen and chloride ions described above. Charge-discharge tests were conducted at room temperature with a current density of 100 mA / g, and the test voltage range was 0–1.2 V.

[0083] Figure 7 The graph shows the cycle performance of the aqueous chloride-ion battery in Comparative Example 1. From... Figure 7 It can be seen that the initial discharge capacity of the aqueous chloride ion battery is 30.81 mAh / g, which increases to 61 mAh / g after 50 cycles.

[0084] Comparative Example 2:

[0085] An aqueous hydrogen-ion battery includes a positive electrode, a negative electrode, and an electrolyte. The active material of the positive electrode is aluminate oxide ZnAl2O4. The electrolyte is a dilute sulfuric acid solution with a concentration of 0.1 mol / L and a pH value of 1.

[0086] In Comparative Example 1, the aluminate oxide ZnAl2O4 used was the aluminate oxide ZnAl2O4 prepared in Example 5.

[0087] Electrochemical performance was tested using a three-electrode simulated battery. The positive electrode was the same as that in Example 5, the counter electrode was a platinum electrode, and the reference electrode was a silver / silver chloride electrode. The electrolyte was the acidic aqueous solution containing hydrogen and chloride ions described above. Charge-discharge tests were conducted at room temperature with a current density of 100 mA / g, and the test voltage range was 0–1.2 V.

[0088] Figure 8 The graph shows the cycle performance of the aqueous hydrogen-ion battery in Comparative Example 2. From... Figure 8 It can be seen that the initial discharge capacity of the aqueous hydrogen ion battery is 66.15 mAh / g, which decreases to 28.1 mAh / g after 50 cycles.

[0089] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make many possible variations and modifications to the technical solutions of the present invention using the methods and techniques disclosed above, or modify them into equivalent embodiments with equivalent changes, without departing from the spirit and technical essence of the present invention. Therefore, any simple modifications, equivalent substitutions, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solutions of the present invention shall still fall within the protection scope of the technical solutions of the present invention.

Claims

1. An aqueous hydrogen-chlorine dual-ion rechargeable battery, comprising a positive electrode, a negative electrode, and an electrolyte, characterized in that, The active material of the positive electrode is an aluminate oxide with the chemical formula MAl2O4, wherein M is at least one of Cu, Mg, and Zn; the electrolyte is an acidic aqueous solution containing hydrogen ions and chloride ions.

2. The aqueous hydrogen-chlorine dual-ion rechargeable battery according to claim 1, characterized in that, The acidic aqueous solution containing hydrogen ions and chloride ions is prepared from chloride, acidic solution and water; the concentration of chloride in the acidic aqueous solution containing hydrogen ions and chloride ions is 0.5 mol / L to 4 mol / L, and the pH value of the acidic aqueous solution containing hydrogen ions and chloride ions is 1 to 6.

3. The aqueous hydrogen-chlorine dual-ion rechargeable battery according to claim 2, characterized in that, The chloride is at least one of a metal chloride and tetramethylammonium chloride, and the metal chloride is at least one of aluminum chloride, magnesium chloride, zinc chloride, copper chloride, manganese chloride, nickel chloride, ferric chloride, lithium chloride, sodium chloride, and potassium chloride; the volume of the acidic solution accounts for 1% to 10% of the total volume of the acidic aqueous solution containing hydrogen ions and chloride ions, the concentration of the acidic solution is 0.1 mol / L to 1 mol / L, and the acidic solution is at least one of acetic acid aqueous solution, hydrochloric acid solution, phosphoric acid solution, carbonic acid solution, and sulfuric acid solution.

4. The aqueous hydrogen-chlorine dual-ion rechargeable battery according to any one of claims 1 to 3, characterized in that, The method for preparing the aluminate oxide includes the following steps: (1) Aluminum salt, metal M salt and water are mixed to obtain a mixed solution; wherein the metal M salt is at least one of copper salt, magnesium salt and zinc salt; (2) Mix the mixed solution obtained in step (1) with the precipitant, adjust the pH value to 6.5-12, carry out the reaction, age, wash and dry to obtain the precursor; (3) The precursor obtained in step (2) is sintered to obtain aluminate oxide.

5. The aqueous hydrogen-chlorine dual-ion rechargeable battery according to claim 4, characterized in that, The total molar concentration of aluminum ions and M ions in the mixed solution is 0.1 mol / L to 4 mol / L, and the molar ratio of the aluminum salt to the metallic M salt is 1:1; the molar ratio of the precipitant to the total molar amount of aluminum ions and M ions in the mixed solution is 4 to 8:

1.

6. The aqueous hydrogen-chlorine dual-ion rechargeable battery according to claim 4, characterized in that, The aluminum salt is at least one of aluminum nitrate, aluminum chloride, aluminum sulfate, and aluminum trifluoromethanesulfonate; the copper salt is at least one of copper sulfate, copper chloride, copper sulfamate, copper bromide, copper nitrate, and copper acetate; the magnesium salt is at least one of magnesium sulfate, magnesium chloride, magnesium sulfamate, magnesium bromide, magnesium nitrate, and magnesium acetate; the zinc salt is at least one of zinc sulfate, zinc chloride, zinc sulfamate, zinc bromide, zinc nitrate, and zinc acetate; and the precipitant is at least one of ammonium bicarbonate, ammonium carbonate, urea, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, oxalic acid, sodium hydroxide, and potassium hydroxide.

7. The aqueous hydrogen-chlorine dual-ion rechargeable battery according to claim 4, characterized in that, In step (1), the mixing is carried out under stirring conditions, the stirring speed is 200 rpm to 2000 rpm, and the mixing temperature is 20℃ to 80℃; And / or, in step (2), the reaction time is 10 min to 60 min, the aging time is 6 h to 24 h, the drying temperature is 60 ° C to 120 ° C, and the drying time is 2 h to 12 h; And / or, in step (3), the sintering temperature is 700℃~1600℃, the sintering time is 2h~96h, and the heating rate during the sintering process is 1℃ / min~15℃ / min.

8. The aqueous hydrogen-chlorine dual-ion rechargeable battery according to any one of claims 1 to 3, characterized in that, The negative electrode material is any one of aluminum, magnesium, zinc, copper, nickel, iron, manganese, silver, lead and carbon materials, and the carbon material is any one of graphite, activated carbon, hard carbon, soft carbon and graphene. The negative electrode material is in the form of foil or powder. The aqueous hydrogen-chlorine dual-ion rechargeable battery also includes a separator.

9. A method for preparing an aqueous hydrogen-chlorine dual-ion rechargeable battery as described in any one of claims 1 to 8, characterized in that, Includes the following steps: S1. Aluminate oxide, conductive agent, binder and solvent are mixed to form slurry A. Slurry A is coated on the positive electrode current collector, and then dried and rolled to form the positive electrode. S2. Mix the negative electrode material, conductive agent and binder to form slurry B, coat slurry B onto the current collector and dry it to form the negative electrode; or, use foil directly as the negative electrode. S3. Assemble the positive electrode obtained in step S1, the negative electrode obtained in step S2, the electrolyte, and the separator to obtain an aqueous hydrogen-chlorine dual-ion rechargeable battery; the electrolyte is an acidic aqueous solution containing hydrogen ions and chloride ions.

10. The method for preparing an aqueous hydrogen-chlorine dual-ion rechargeable battery according to claim 9, characterized in that, In step S1, the mass ratio of the aluminate oxide, conductive agent, and binder is 70-94:15-3:15-3, and the positive electrode current collector is any one of copper foil, copper mesh, titanium foil, titanium mesh, molybdenum foil, and carbon paper. In step S2, the mass of the conductive agent accounts for 2% to 10% of the total mass of slurry B, and the mass of the binder accounts for 2% to 10% of the total mass of slurry B.

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