Zinc metal battery capable of reconstructing zinc-loving interface and preparation method of zinc metal battery

Abstract

The invention provides a zinc metal battery with a reconfigurable zinc-philic interface and a preparation method thereof, and belongs to the technical field of zinc metal batteries. The zinc metal battery comprises a copper-plated zinc sheet electrode and a specific electrolyte system, the electrolyte system comprises soluble zinc salt, a complexing agent having a strong complexing effect with copper ions, a pH regulator and a surfactant, and the pH regulator is adopted to regulate the pH of the electrolyte system to weak acidity. According to the method, a specific electrolyte system and the copper-plated zinc sheet electrode are cooperatively used, dissolution of copper atoms in a plating layer is promoted in the battery circulation process, active copper sites can be continuously exposed in the dissolution-redeposition process of the copper atoms, the microtopography of the surface of the electrode can be continuously reconstructed, the interface environment of a low nucleation energy barrier can be maintained, and the performance of the battery is improved. Therefore, the static failure limitation of a traditional coating is broken through, the nucleation regulation and control effect of the copper alloy layer can be exerted for a long time, and a new interface engineering strategy is provided for development of a high-performance zinc-based energy storage device.

Description

Technical Field

[0001] The present invention relates to the technical field of zinc metal batteries, and in particular to a zinc metal battery with a reconfigurable zinc-philic interface and a preparation method thereof. Background Art

[0002] The theoretical capacity of zinc metal anodes is as high as 820 mAh / g, and they have a low redox potential (-0.76 V vs. SHE). However, their practical application is still limited by bottlenecks such as uncontrollable dendrite growth, hydrogen evolution corrosion, and interface passivation. In recent years, interface engineering strategies have become a research hotspot for solving zinc anode problems. Among them, the introduction of a copper-containing interface layer can effectively reduce the nucleation overpotential of zinc and regulate the uniform deposition behavior of zinc, which is a simple and effective improvement strategy. However, current interface engineering strategies mostly focus on the static design of the interface layer and are difficult to dynamically adapt to the complex evolution process of the electrode / electrolyte interface. Copper-plated zinc anodes face the same problem. The main problem is that the high standard electrode potential of copper (+0.337 V vs. SHE) makes it difficult for it to participate in the electrochemical stripping process. The copper sites on the electrode surface are easily covered by zinc deposits or byproducts during the cycle, resulting in the passivation of the copper sites and the inability to maintain the interface regulation function in the long term. Summary of the Invention

[0003] To address the shortcomings of the prior art, the present invention provides a zinc metal battery with a reconfigurable zinc-philic interface and a method for preparing the same. By synergizing copper-coated zinc sheets with a specific electrolyte system, the present invention significantly extends the cycle life of the zinc metal battery, resulting in excellent cycling stability.

[0004] To achieve the above purpose, the specific technical solutions of the present invention are as follows:

[0005] The present invention provides a zinc metal battery with a reconfigurable zinc-friendly interface, comprising a copper-zinc plated electrode and an electrolyte system, wherein the electrolyte system comprises a soluble zinc salt, a copper ion (Cu 2+ ) a complexing agent, a pH regulator and a surfactant with strong complexing effect, and the pH regulator is used to adjust the pH of the electrolyte system to a weak acidity; the present invention uses a specific electrolyte system in conjunction with a copper-zinc plated sheet electrode to achieve reconstruction of zinc-philic copper sites during battery cycling, thereby significantly improving the cycle stability and service life of the zinc metal battery.

[0006] The present invention prepares an electrolyte system with synergistic functionality by introducing a chelating agent and a surfactant that have a strong chelating effect with copper ions into the electrolyte system, and adjusting the pH of the electrolyte system to a weakly acidic environment using an organic acid. The electrolyte system is used in conjunction with a copper-zinc plated sheet electrode in a zinc metal battery. During the battery cycle, the dissolution of copper atoms in the coating can be promoted. The dissolution-redeposition process of the copper atoms not only continuously exposes the active copper sites, but also continuously reconstructs the micromorphology of the electrode surface, maintaining an interface environment with a low nucleation energy barrier, thereby breaking through the static failure limit of traditional coatings and enabling the nucleation regulation effect of the copper alloy layer to be exerted in a long-term manner, providing a new interface engineering strategy for the development of high-performance zinc-based energy storage devices.

[0007] Furthermore, the pH of the electrolyte system is 3-4.

[0008] Furthermore, the preparation method of the copper-zinc plated electrode is as follows:

[0009] A copper chloride (CuCl2) solution is prepared using an alcohol solvent as the plating solution. The zinc foil is immersed in the plating solution, left to stand for 30 to 90 seconds, then taken out and transferred to an oleic acid ethanol solution and immersed for another 30 to 90 seconds; then washed and dried to obtain a copper-zinc sheet electrode, in which the coating is a 1 to 5 micron thick layer of tightly stacked copper alloy particles, the main component of which is a CuZn5 alloy with a low copper content.

[0010] The present invention prepares a copper-plated zinc sheet electrode by chemical immersion plating, specifically by immersing the zinc sheet in an alcohol-based copper chloride solution, and uniformly depositing copper ions on the surface of the zinc substrate in the form of a copper alloy through in-situ reduction, forming a densely stacked copper alloy particle layer. The cycle performance of a zinc metal battery assembled with this electrode and an ordinary aqueous electrolyte is not outstanding, but when this electrode is used in conjunction with the specific electrolyte system of the present invention, the zinc metal battery can exhibit significantly improved cycle stability and service life. The present invention achieves long-term in-situ alloy interface regulation by introducing a complexing agent that has a strong complexing effect with copper ions into the electrolyte system, and the complexing agent synergizes with the copper-plated zinc sheet electrode. The complexing agent that has a strong complexing effect with copper ions can promote the dynamic redissolution process of copper atoms, effectively solving the performance degradation problem caused by the passivation of copper sites on the electrode surface. This in-situ surface continuous renewal and reconstruction of copper sites mechanism breaks through the traditional coating failure limitations and effectively avoids passivation failure. For the electrolyte system, the present invention uses an organic acid pH regulator to adjust the pH of the electrolyte system to a weak acid environment, so that the complexing agent with strong complexing effect with copper ions can better play the above synergistic function. At the same time, the organic acid pH regulator contains 2+The strong complexing groups further promote the electrochemical dissolution of copper atoms, effectively improving the overall performance of the battery. Furthermore, the surfactants introduced into the electrolyte system further optimize the electrolyte system, effectively alleviating the problem of excessive voltage polarization caused by the copper-zinc-plated sheet electrodes. By synergizing the copper-zinc-plated electrodes with a specific electrolyte system, the present invention significantly improves the cycle life of zinc metal batteries, effectively alleviating the failure of static coatings and providing a new direction for the development of long-lasting and stable zinc-based energy storage devices.

[0011] Furthermore, the concentration of copper chloride in the plating solution is 0.05-0.2 M.

[0012] Furthermore, the alcohol solvent includes but is not limited to at least one of ethanol, ethylene glycol, isopropanol, and n-butanol.

[0013] Furthermore, the concentration of the oleic acid ethanol solution is 1-3 vol.%.

[0014] Furthermore, after removing the electrode from the plating solution, it must be completely immersed in an oleic acid ethanol solution within 1 to 2 seconds to remove dirt and oxides on the surface of the alloy layer and form a surface film that is resistant to oxidation in the air environment; if it is exposed to air for too long, the surface will become dark and oxidized, seriously affecting the uniformity of the plating layer, making the electrode rough, which is not conducive to the uniform deposition of zinc.

[0015] Furthermore, the copper-zinc plated sheet electrode is dried in the shade at room temperature for 1-3 hours. In the present invention, the drying method has a significant impact on the performance of the copper-zinc plated sheet. If it is dried under heating conditions, cracks and defects will appear in the coating, which will reduce the electrochemical performance of the electrode.

[0016] Furthermore, the concentration of the soluble zinc salt in the electrolyte system is 2-3 M.

[0017] Furthermore, the concentration of the complexing agent in the electrolyte system is 0.18~0.58M.

[0018] Furthermore, the concentration of the surfactant in the electrolyte system is 1-3 mM.

[0019] Furthermore, the soluble zinc salt includes but is not limited to at least one of zinc sulfate, zinc bromide, zinc nitrate, zinc acetate, zinc trifluoromethanesulfonate, and zinc citrate.

[0020] Furthermore, the complexing agent is ethylenediaminetetraacetic acid (EDTA) salt.

[0021] Furthermore, the EDTA salt includes but is not limited to at least one of EDTA ammonium salt, EDTA sodium salt, and EDTA potassium salt.

[0022] Furthermore, the ammonium salt of EDTA includes but is not limited to tetraammonium EDTA; the sodium salt of EDTA includes but is not limited to disodium EDTA, tetrasodium EDTA, sodium ferric EDTA, and sodium magnesium EDTA; the potassium salt of EDTA includes but is not limited to dipotassium EDTA, tripotassium EDTA, and tetrapotassium EDTA.

[0023] Furthermore, the pH adjuster is an organic acid. The copper-zinc plated electrode alloy layer is easily passivated in an alkaline environment. By adding an organic acid to the electrolyte system and adjusting the pH of the electrolyte system to between 3 and 4, the present invention can effectively promote the anodic oxidation and dissolution of the copper element in the copper-zinc plated electrode alloy layer. At the same time, the organic acid contains complexing groups with complexing effects, which can further maintain the stability of the battery.

[0024] Furthermore, the organic acid includes but is not limited to at least one of ethylenediaminetetraacetic acid, acetic acid, citric acid, and ascorbic acid.

[0025] Furthermore, the surfactant includes, but is not limited to, at least one of sodium lauryl sulfate, sodium lauryl phosphate, sodium laureth sulfate, sodium dodecylbenzenesulfonate, α-olefin sulfonate, dioctyl sodium sulfosuccinate, hexadecyltrimethylammonium bromide, and Triton X-100. The present invention reduces interfacial impedance by increasing the electrolyte / electrode microscopic contact surface by adding a surfactant to the electrolyte system, thereby improving the high polarization voltage caused by the copper alloy electrode.

[0026] The present invention also provides a method for preparing the zinc metal battery with a reconfigurable zinc-philic interface, comprising the following steps:

[0027] A soluble zinc salt aqueous solution is prepared; a complexing agent having a strong complexing effect with copper ions is added to the soluble zinc salt aqueous solution and mixed evenly, and a pH regulator is used to adjust the pH of the solution to between 3 and 4; a surfactant is added and mixed evenly to obtain an electrolyte system;

[0028] A 0.05-0.2 M copper chloride solution is prepared using an alcohol solvent as the plating solution. The zinc foil is immersed in the plating solution and allowed to stand for 30-90 seconds before being removed and transferred to a 1-3 vol.% oleic acid ethanol solution and immersed for another 30-90 seconds. The foil is then washed and dried to obtain a copper-zinc plated electrode.

[0029] The copper-coated zinc sheet electrode, separator and electrolyte system are assembled to obtain a zinc metal battery with a reconfigurable zinc-philic interface.

[0030] Compared with the prior art, the present invention is beneficial in that:

[0031] The present invention introduces a complexing agent with a strong complexing effect with copper ions into the electrolyte system. The complexing agent with a strong complexing effect with copper ions synergistically acts with the copper-zinc plated electrode to achieve an electrochemical dissolution-redeposition cycle of copper atoms in the copper plating layer, continuously renewing and reconstructing the copper sites on the electrode surface, avoiding the passivation failure of the zinc-philic plating layer, and thus enabling long-term regulation of zinc deposition. At the same time, the present invention uses an organic acid pH regulator to adjust the pH of the electrolyte system to a weak acid environment. The organic acid pH regulator also contains a 2+ The group has a strong complexing effect, which further promotes the electrochemical dissolution of copper atoms. In addition, the surfactant introduced into the electrolyte system of the present invention effectively improves the problem of excessive voltage polarization caused by the copper-zinc plated electrode. The electrolyte system provided by the present invention, which cooperates with the copper-zinc plated electrode, greatly improves the cycle life of zinc metal batteries, effectively improves the failure of static coatings, and provides a new direction for the development of long-lasting and stable zinc-based energy storage devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a scanning electron micrograph of the copper-zinc plated electrode in Example 1;

[0033] Figure 2 is the XRD pattern of the copper-zinc plate electrode in Example 1;

[0034] Figure 3 The cycling stability test results of the button-type Zn||Zn symmetrical battery in Example 1 are shown;

[0035] Figure 4 The cycling stability test results of the button-type Zn||Zn symmetrical battery in Example 2 are shown;

[0036] Figure 5 The cycling stability test results of the button-type Zn||Zn symmetrical battery in Example 3 are shown;

[0037] Figure 6 The cycling stability test results of the button-type Zn||Zn symmetrical battery in Comparative Example 1 are shown;

[0038] Figure 7 The cycling stability test results of the button-type Zn||Zn symmetrical battery in Comparative Example 2 are shown;

[0039] Figure 8 This is the cycle stability test result of the button-type Zn||Zn symmetrical battery in Comparative Example 3. DETAILED DESCRIPTION

[0040] The technical solutions of the present invention are described clearly and completely below. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. All other embodiments obtained by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0041] The present invention provides a zinc metal battery with a reconfigurable zinc-friendly interface, comprising a copper-zinc plated electrode and an electrolyte system, wherein the electrolyte system comprises a soluble zinc salt, a copper ion (Cu 2+ ) a complexing agent, a pH regulator and a surfactant with strong complexing effect, and the pH regulator is used to adjust the pH of the electrolyte system to a weak acidity; the present invention realizes the reconstruction of zinc-philic copper sites during the battery cycle process by using a specific electrolyte system in conjunction with a copper-zinc plated sheet electrode.

[0042] In some examples, the pH of the electrolyte system is 3-4.

[0043] In some examples, the copper-zinc plated sheet electrode is prepared as follows: a copper chloride (CuCl2) solution with a concentration of 0.05-0.2 M is prepared using an alcohol solvent as a plating solution, the zinc foil is immersed in the plating solution, allowed to stand for 30-90 seconds, then removed, and within 1-2 seconds, transferred to a 1-3 vol.% oleic acid ethanol solution and immersed for another 30-90 seconds; the foil is then rinsed and air-dried at room temperature in a shaded area for 1-3 hours to obtain the copper-zinc plated sheet electrode. The alcohol solvent includes, but is not limited to, at least one of ethanol, ethylene glycol, isopropyl alcohol, and n-butanol.

[0044] In some examples, the concentration of the soluble zinc salt in the electrolyte system is 2-3 M, the concentration of the complexing agent is 0.18-0.58 M, and the concentration of the surfactant is 1-3 mM.

[0045] In some examples, the soluble zinc salt includes but is not limited to at least one of zinc sulfate, zinc bromide, zinc nitrate, zinc acetate, zinc trifluoromethanesulfonate, and zinc citrate; the complexing agent is an ethylenediaminetetraacetic acid (EDTA) salt, and the EDTA salt includes but is not limited to at least one of EDTA ammonium salt, EDTA sodium salt, and EDTA potassium salt; the EDTA ammonium salt includes but is not limited to EDTA tetraammonium; the EDTA sodium salt includes but is not limited to EDTA disodium, EDTA tetrasodium, EDTA diso ... The present invention relates to a novel surfactant comprising the following: sodium ferric phosphate, sodium magnesium EDTA; the potassium salt of EDTA includes but is not limited to dipotassium EDTA, tripotassium EDTA, and tetrapotassium EDTA; the pH regulator is an organic acid, and the organic acid includes but is not limited to at least one of EDTA, acetic acid, citric acid, and ascorbic acid; the surfactant includes but is not limited to at least one of sodium lauryl sulfate, sodium lauryl phosphate, sodium laureth sulfate, sodium dodecylbenzenesulfonate, α-olefin sulfonate, sodium dioctyl sulfosuccinate, hexadecyltrimethylammonium bromide, and Triton X-100.

[0046] In the following specific embodiments, the method for preparing the zinc metal battery with a reconfigurable zinc-philic interface comprises the following steps:

[0047] A soluble zinc salt aqueous solution is prepared; a complexing agent with a strong complexing effect with copper ions is added to the soluble zinc salt aqueous solution and mixed evenly, and the pH of the solution is adjusted to between 3 and 4 using a pH adjuster; a surfactant is added and mixed evenly to obtain an electrolyte system; a copper chloride solution with a concentration of 0.05 to 0.2 M is prepared using an alcohol solvent as a plating solution, a zinc foil is immersed in the plating solution, allowed to stand for 30 to 90 seconds, then removed and transferred to a 1 to 3 vol.% oleic acid ethanol solution and immersed for another 30 to 90 seconds; the foil is washed and dried to obtain a copper-zinc plated sheet electrode; the copper-zinc plated sheet electrode, a separator and an electrolyte system are assembled to obtain a zinc metal battery having zinc-philic copper sites that can be reconstructed during battery cycling.

[0048] Example 1

[0049] A zinc metal battery with a reconfigurable zinc-philic interface, the preparation method is as follows:

[0050] 1. Preparation of copper-zinc plated electrode

[0051] (1) Prepare commercial pure zinc foil with a thickness of 0.1 mm, polish it to 8000 mesh with sandpaper, ultrasonically clean it with deionized water and ethanol for 30 minutes, and then place it in an oven at 60°C to dry it for use;

[0052] (2) Weigh 0.341 g of copper chloride dihydrate into a container, add anhydrous ethanol to make the total volume reach 40 mL, and stir at room temperature for 20 minutes to prepare a light green transparent ethanol copper chloride solution as a plating solution;

[0053] (3) Dissolve 2 mL of oleic acid in 98 mL of ethanol and stir at room temperature for 5 minutes to prepare a 2 vol.% oleic acid ethanol solution;

[0054] (4) Place the prepared zinc foil in a culture dish and slowly pour the prepared plating solution into it, completely immersing the zinc foil. After reacting for 50 seconds, the surface color of the zinc foil changes, and its shiny surface turns dark yellow. Clip out the zinc foil and transfer the copper-plated zinc foil to a container containing 2 vol.% oleic acid ethanol solution within 2 seconds. Continue soaking for 60 seconds, take it out and place it in a shaded place for 1 hour to obtain the copper-plated zinc foil. Use a sheet punching machine to punch it into a disc with a diameter of 10 mm, thus obtaining a copper-plated zinc sheet electrode.

[0055] Figure 1 This is a scanning electron micrograph of the copper-zinc plated sheet electrode obtained in Example 1. As can be seen from the figure, the surface of the copper-zinc plated sheet electrode is a dense layer of micron-sized particles stacked together, without cracks or defects. Figure 2 This is the XRD pattern of the copper-zinc plated sheet electrode obtained in Example 1. It can be seen from the figure that the main component of the copper-zinc plated sheet electrode is CuZn5 alloy.

[0056] 2. Preparation of electrolyte system for use with copper-zinc plated sheet electrodes

[0057] (1) Prepare a 2.5 M zinc sulfate aqueous solution as the main electrolyte;

[0058] (2) Mix 5.5 g of EDTA with 6 mL of ammonia water (25-28 wt.%) and stir at room temperature for 1 h to prepare 10 mL of a transparent EDTA tetraammonium solution as a complexing agent;

[0059] (3) Add 3 mL of the prepared tetraammonium salt of ethylenediaminetetraacetic acid solution to 17 mL of the electrolyte body and stir at room temperature for 5 minutes to obtain an electrolyte containing a complexing agent;

[0060] (4) Add ethylenediaminetetraacetic acid to the electrolyte containing the complexing agent, stir at room temperature for 1 h, and adjust the pH of the electrolyte to between 3 and 4;

[0061] (5) 0.012 g of sodium dodecyl sulfate was added to the pH-adjusted electrolyte containing the complexing agent, and the mixture was stirred at room temperature for 5 minutes to obtain an electrolyte for use with the copper-zinc plated electrode.

[0062] 3. Assembly of zinc metal batteries

[0063] A button-type Zn||Zn symmetric battery was assembled by assembling a copper-zinc sheet electrode, a 1.6 cm diameter / 1 mm thick glass fiber paper, and 150 μL of electrolyte used in conjunction with the copper-zinc sheet electrode. -2 (1 mAh cm -2 ) to test the cycle life and cycle stability, the test results are as follows Figure 3 The test results show that the button-type Zn||Zn symmetrical battery of Example 1 can be stably cycled for more than 1620 h.

[0064] Example 2

[0065] A zinc metal battery with a reconfigurable zinc-philic interface, wherein the preparation of the copper-zinc plated sheet electrode is the same as that in Example 1.

[0066] The preparation method of the electrolyte system used in conjunction with the copper-zinc plated sheet electrode in this embodiment is as follows:

[0067] (1) Prepare a 2.5 M zinc sulfate aqueous solution as the main electrolyte;

[0068] (2) Add 2.35 g of tetrasodium ethylenediaminetetraacetate to 20 mL of the electrolyte body and stir at room temperature for 10 minutes to obtain an electrolyte containing a complexing agent;

[0069] (3) Add ethylenediaminetetraacetic acid to the electrolyte containing the complexing agent, stir at room temperature for 1 h, and adjust the pH of the electrolyte to between 3 and 4;

[0070] (4) 0.012 g of sodium dodecyl sulfate was added to the pH-adjusted electrolyte containing the complexing agent, and the mixture was stirred at room temperature for 5 minutes to obtain an electrolyte for use with the copper-zinc plated electrode.

[0071] A button-type Zn||Zn symmetric battery was assembled by assembling a copper-zinc sheet electrode, a 1.6 cm diameter / 1 mm thick glass fiber paper, and 150 μL of electrolyte used in conjunction with the copper-zinc sheet electrode. -2 (1 mAh cm -2 ) to test the cycle life and cycle stability, the test results are as follows Figure 4 The test results show that the button-type Zn||Zn symmetrical battery of Example 2 can be stably cycled for more than 1020 h.

[0072] Example 3

[0073] A zinc metal battery with a reconfigurable zinc-philic interface, wherein the preparation of the copper-zinc plated sheet electrode is the same as that in Example 1.

[0074] The preparation method of the electrolyte system used in conjunction with the copper-zinc plated sheet electrode in this embodiment is as follows:

[0075] (1) Prepare a 2.5 M zinc sulfate aqueous solution as the main electrolyte;

[0076] (2) Mix 5.5 g of EDTA with 6 mL of ammonia water (25-28 wt.%) and stir at room temperature for 1 h to prepare 10 mL of a transparent EDTA tetraammonium solution as a complexing agent;

[0077] (3) Add 3 mL of the prepared ethylenediaminetetraacetic acid tetraammonium salt solution to 17 mL of the electrolyte body and stir at room temperature for 5 minutes to obtain an electrolyte containing a complexing agent;

[0078] (4) Add citric acid to the electrolyte containing the complexing agent, stir at room temperature for 1 h, and adjust the pH of the electrolyte to between 3 and 4;

[0079] (5) 0.012 g of sodium dodecyl sulfate was added to the pH-adjusted electrolyte containing the complexing agent, and the mixture was stirred at room temperature for 5 minutes to obtain an electrolyte for use with the copper-zinc plated electrode.

[0080] A button-type Zn||Zn symmetric battery was assembled by assembling a copper-zinc sheet electrode, a 1.6 cm diameter / 1 mm thick glass fiber paper, and 150 μL of electrolyte used in conjunction with the copper-zinc sheet electrode. -2 (1 mAh cm -2 ) to test the cycle life and cycle stability, the test results are as follows Figure 5 The test results show that the button-type Zn||Zn symmetrical battery of Example 3 can be stably cycled for more than 1020 h.

[0081] Comparative Example 1

[0082] A zinc metal battery, the preparation of its copper-zinc plated sheet electrode is the same as that in Example 1.

[0083] The preparation method of the electrolyte in this comparative example is as follows: a zinc sulfate aqueous solution with a concentration of 2.5 M is prepared as the electrolyte.

[0084] A button-type Zn||Zn symmetrical battery was assembled by assembling a copper-zinc plate electrode, a 1.6 cm diameter / 1 mm thick glass fiber paper, and 150 μL electrolyte. -2 (1 mAh cm -2 ) to test the cycle life and cycle stability, the test results are as follows Figure 6The test results show that the button-type Zn||Zn symmetric battery of Comparative Example 1 suffered a short-circuit failure after only 138 h of stable cycling, indicating that the electrode copper layer only played a role in regulating zinc deposition in the early stages of cycling. This highlights the advantage of the synergistically functional electrolyte in the present invention in promoting the dissolution-redeposition process of the plated copper atoms. The dissolution-redeposition process allows copper sites to be continuously renewed and exposed on the surface, achieving the function of maintaining a low nucleation barrier interface for a long time.

[0085] Comparative Example 2

[0086] A zinc metal battery, the preparation of its copper-zinc plated sheet electrode is the same as that in Example 1.

[0087] The preparation method of the electrolyte in this comparative example is:

[0088] (1) Prepare a 2.5 M zinc sulfate aqueous solution as the main electrolyte;

[0089] (2) Mix 5.5 g of EDTA with 6 mL of ammonia water (25-28 wt.%) and stir at room temperature for 1 h to prepare 10 mL of a transparent EDTA tetraammonium solution as a complexing agent;

[0090] (3) Add 3 mL of the prepared tetraammonium salt of ethylenediaminetetraacetic acid solution to 17 mL of the electrolyte body and stir at room temperature for 5 minutes to obtain the electrolyte.

[0091] A button-type Zn||Zn symmetrical battery was assembled by assembling a copper-zinc plate electrode, a 1.6 cm diameter / 1 mm thick glass fiber paper, and 150 μL electrolyte. -2 (1 mAh cm -2 ) to test the cycle life and cycle stability, the test results are as follows Figure 7 The test results show that the stable cycle time of the button-type Zn||Zn symmetric battery of Comparative Example 2 is extended to 230 h, but it is still significantly lower than the zinc metal batteries prepared in Examples 1, 2, and 3 of the present invention. This confirms that the non-weakly acidic environment cannot effectively exert the function of the complexing agent in the electrolyte to promote the redissolution of copper atoms, and thus cannot effectively improve the cycle stability performance of the battery.

[0092] Comparative Example 3

[0093] A zinc metal battery, the preparation of its copper-zinc plated sheet electrode is the same as that in Example 1.

[0094] The preparation method of the electrolyte in this comparative example is:

[0095] (1) Prepare a 2.5 M zinc sulfate aqueous solution as the main electrolyte;

[0096] (2) Mix 5.5 g of EDTA with 6 mL of ammonia water (25-28 wt.%) and stir at room temperature for 1 h to prepare 10 mL of a transparent EDTA tetraammonium solution as a complexing agent;

[0097] (3) Add 3 mL of the prepared tetraammonium salt of ethylenediaminetetraacetic acid solution to 17 mL of the electrolyte body and stir at room temperature for 5 minutes to obtain an electrolyte containing a complexing agent;

[0098] (4) Add 0.012 g of sodium dodecyl sulfate to the electrolyte containing the complexing agent and stir at room temperature for 5 minutes to obtain an electrolyte.

[0099] A button-type Zn||Zn symmetrical battery was assembled by assembling a copper-zinc plate electrode, a 1.6 cm diameter / 1 mm thick glass fiber paper, and 150 μL electrolyte. -2 (1 mAh cm -2 ) to test the cycle life and cycle stability, the test results are as follows Figure 8 The test results show that the charge-discharge curves of the button-type Zn||Zn symmetrical battery in Comparative Example 3 show a further decrease in polarization voltage and an increase in cycle life relative to Comparative Example 2 after the addition of a surfactant. This confirms that the trace amount of surfactant added to the electrolyte system of the present invention can effectively improve the problem of excessive voltage polarization caused by the copper-zinc plated sheet electrode.

[0100] In summary, the zinc metal battery provided by the present invention comprises a copper-plated zinc sheet electrode and an electrolyte system, wherein the electrolyte system comprises a soluble zinc salt, a complexing agent having a strong complexing effect with copper ions, a pH regulator and a surfactant, and the pH regulator is used to adjust the pH of the electrolyte system to a weak acidity; the present invention achieves the reconstruction of zinc-philic copper sites during the battery cycle by synergistically using the above specific electrolyte system with the copper-plated zinc sheet electrode, thereby significantly improving the cycle stability and service life of the zinc metal battery.

[0101] The above specific embodiments describe the implementation of the present invention in detail, but the present invention is not limited to the specific details of the above embodiments. Within the scope of the claims and technical concept of the present invention, various simple modifications and changes can be made to the technical solution of the present invention, and these simple modifications all fall within the scope of protection of the present invention.

Claims

1. A zinc metal battery with a reconfigurable zinc-philic interface, characterized in that: By using an electrolyte system in conjunction with a copper-zinc-plated sheet electrode, reconstruction of the zinc-philic copper sites in the plating layer during battery cycling is achieved. The electrolyte system includes a soluble zinc salt, a complexing agent with a strong complexing effect with copper ions, a pH regulator, and a surfactant. The pH regulator is used to adjust the pH of the electrolyte system to a weak acidity.

2. The zinc metal battery with a reconfigurable zinc-philic interface according to claim 1, characterized in that The pH of the electrolyte system is 3-4.

3. The zinc metal battery with a reconfigurable zinc-philic interface according to claim 1, characterized in that The preparation method of the copper-zinc plated sheet electrode is as follows: Prepare a copper chloride solution as a plating solution, soak the zinc foil in the plating solution for 30-90 seconds, then transfer it to an oleic acid ethanol solution and continue soaking for 30-90 seconds; then wash and dry it to obtain a copper-zinc plated sheet electrode.

4. The zinc metal battery with a reconfigurable zinc-philic interface according to claim 3, characterized in that The concentration of copper chloride in the plating solution is 0.05-0.2 M, and the concentration of the oleic acid ethanol solution is 1-3 vol.%.

5. The zinc metal battery with a reconfigurable zinc-philic interface according to claim 3, characterized in that The copper-zinc plated electrode is dried in the shade at room temperature for 1-3 hours.

6. The zinc metal battery with a reconfigurable zinc-philic interface according to claim 1, characterized in that In the electrolyte system, the concentration of the soluble zinc salt is 2-3 M, the concentration of the complexing agent is 0.18-0.58 M, and the concentration of the surfactant is 1-3 mM.

7. The zinc metal battery with a reconfigurable zinc-philic interface according to claim 1, characterized in that The soluble zinc salt includes but is not limited to at least one of zinc sulfate, zinc bromide, zinc nitrate, zinc acetate, zinc trifluoromethanesulfonate, and zinc citrate; the complexing agent includes ethylenediaminetetraacetate; the pH regulator includes an organic acid; and the surfactant includes but is not limited to at least one of sodium lauryl sulfate, sodium lauryl phosphate, sodium laureth sulfate, sodium dodecylbenzenesulfonate, α-olefin sulfonate, dioctyl sodium sulfosuccinate, hexadecyltrimethylammonium bromide, and Triton X-100.

8. The zinc metal battery with a reconfigurable zinc-philic interface according to claim 7, characterized in that The EDTA salt includes but is not limited to at least one of EDTA ammonium salt, EDTA sodium salt, and EDTA potassium salt.

9. The zinc metal battery with a reconfigurable zinc-philic interface according to claim 7, characterized in that The organic acid includes but is not limited to at least one of ethylenediaminetetraacetic acid, acetic acid, citric acid, and ascorbic acid.

10. The method for preparing a zinc metal battery with a reconfigurable zinc-philic interface according to any one of claims 1 to 9, characterized in that: The following steps are involved: A soluble zinc salt aqueous solution is prepared; a complexing agent having a strong complexing effect with copper ions is added to the soluble zinc salt aqueous solution and mixed evenly, and a pH regulator is used to adjust the pH of the solution to between 3 and 4; a surfactant is added and mixed evenly to obtain an electrolyte system; A copper chloride solution is prepared as a plating solution; the zinc foil is immersed in the plating solution for 30 to 90 seconds, then transferred to an oleic acid ethanol solution and immersed for another 30 to 90 seconds; the foil is washed and dried to obtain a copper-zinc plated electrode; The copper-coated zinc sheet electrode, separator and electrolyte system are assembled to obtain a zinc metal battery with a reconfigurable zinc-philic interface.

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