Zinc negative electrode with composite interface structure as well as sonochemical preparation method and application of zinc negative electrode

Abstract

The invention provides a zinc negative electrode with a composite interface structure and an ultrasonic chemical preparation method and application thereof, and belongs to the technical field of zinc-based batteries. According to the sonochemical preparation method of the zinc negative electrode with the composite interface structure, the zinc substrate is placed in the oxidizing solution to be subjected to the oxidation-reduction reaction under the ultrasonic condition, the cavitation effect generated by ultrasound can greatly activate electrolyte salt, the mass transfer process is enhanced, and the electrochemical performance of the zinc negative electrode is improved. And a chemical reaction which is difficult to occur or is slowly carried out under a conventional condition is excited, and a composite interface structure consisting of two or more metal elementary substances and / or compounds is formed on the surface of the zinc matrix, so that the interface stability of the zinc negative electrode is improved, and the cycle life of the zinc-based battery is prolonged.

Description

Technical Field

[0001] This invention relates to the field of zinc-based battery technology, specifically to a zinc anode with a composite interface structure and its ultrasonic chemical preparation method and application. Background Technology

[0002] Aqueous zinc-based batteries using zinc as the negative electrode have attracted widespread attention due to their enormous potential in energy storage. This potential stems from their inherent safety, cost-effectiveness, environmental sustainability, and ease of installation. However, the uneven distribution of electrons and ions near the zinc negative electrode can lead to uneven zinc deposition and growth, potentially causing short-circuit failure. Furthermore, corrosion and hydrogen evolution caused by reactions between zinc and water molecules during chemical and electrochemical processes are also key bottlenecks hindering the commercial deployment of zinc-based batteries. Therefore, effectively suppressing dendrite growth while improving the stability between the zinc negative electrode and the electrolyte is a crucial scientific challenge for achieving reliable zinc-based batteries with high efficiency, high stability, and long cycle life.

[0003] To address the aforementioned shortcomings, methods such as electrolyte optimization, anode alloying, and interface layer modification are commonly employed. Among these, interface layer modification has received significant attention due to its substantial protective capabilities and feasibility. However, traditional single-component interface layers inevitably sacrifice certain electrochemical properties of the zinc anode, such as the presence of side reactions or exacerbated polarization. Therefore, the strategy of constructing composite interface layers has gradually been proposed, aiming to combine the advantages of composite materials to improve the uniformity of the interfacial electric field and concentration field during redox reactions, thereby extending the cycle life of the anode.

[0004] In existing technologies, the construction of composite interface layers on the surface of zinc anodes typically involves a spontaneous redox reaction between the zinc anode and an oxidizing solution, or in-situ formation on the zinc anode surface through the decomposition or chemical reaction of a substance during electrochemical cycling. Reactions occurring through spontaneous redox reactions or electrochemical cycling are susceptible to the uniformity of film formation due to changes in solution concentration, ultimately leading to unstable interface layer properties and an inability to effectively improve the cycle life of the anode. Summary of the Invention

[0005] The purpose of this invention is to provide a zinc anode with a composite interface structure, its ultrasonic chemical preparation method, and its application. The cavitation effect generated under ultrasonic conditions can greatly activate the reactants, enhance the mass transfer process, and stimulate chemical reactions that are difficult to occur or proceed slowly under conventional conditions. A composite interface structure composed of two or more different insoluble materials is formed on the surface of the zinc substrate. This composite interface structure is stable and can effectively improve the cycle life of zinc-based batteries.

[0006] To achieve the objectives of this invention, the following technical solutions are provided: A method for ultrasonic chemical preparation of zinc anode with a composite interface structure includes the following steps: A zinc substrate is placed in an oxidizing solution and subjected to a redox reaction under ultrasonic conditions. During the redox reaction, a composite interface structure is constructed on the surface of the zinc substrate, resulting in a zinc anode with a composite interface structure. The oxidizing solution includes an electrolyte salt and a solvent.

[0007] Preferably, the frequency of the ultrasound is 1~60kHz and the power density is 1~300W / cm². 3 The duration is 1 minute to 8 hours; the ultrasound mode is either start-stop mode or continuous mode.

[0008] Preferably, the cation in the electrolyte salt is a metal ion that can undergo a displacement reaction with zinc; the anion in the electrolyte salt is an anion that can react with water molecules or decompose itself.

[0009] Preferably, the oxidizing solution further includes an auxiliary agent; Preferably, the additive is an organic or inorganic material that is soluble in the solvent; or an organic or inorganic material that is insoluble in the solvent.

[0010] Preferably, when the oxidizing solution includes an electrolyte salt and an auxiliary agent, the mass fraction of the auxiliary agent is 0.5-15%.

[0011] The present invention also provides a zinc anode with a composite interface structure prepared by the ultrasonic chemical preparation method of the zinc anode described above, comprising a zinc substrate and a composite interface structure layer in situ constructed on the surface of the zinc substrate; The composite interface structure layer is composed of two or more elemental metals and / or compounds.

[0012] The present invention also provides the application of the zinc anode with the composite interface structure described in the above technical solution in zinc-based batteries.

[0013] This invention provides an ultrasonic chemical preparation method for a zinc anode with a composite interface structure, comprising the following steps: placing a zinc substrate in an oxidizing solution and performing a redox reaction under ultrasonic conditions. During the redox reaction, a composite interface structure is constructed on the surface of the zinc substrate, resulting in the zinc anode with the composite interface structure. The oxidizing solution includes an electrolyte salt and a solvent. This invention introduces cavitation and acoustic flow effects through ultrasound in an electrolyte salt liquid phase solution environment, thereby constructing a fine and uniform composite interface structure in situ on a metallic zinc substrate. The preparation method of this invention has a simple operation process, can prepare the composite interface layer in one step, shortens the preparation time, and the prepared composite structure can be finely controlled by changing the ultrasonic parameters, thus achieving high-efficiency and precise controllable preparation of the zinc anode composite interface structure. Furthermore, the cavitation effect introduced by ultrasound in this invention can promote the diffusion of electrolyte salts and / or additives in oxidizing solutions, thereby preparing a fine and uniform composite interface structure. Secondly, ultrasound conditions can stimulate chemical reactions that are difficult to occur or proceed slowly under non-ultrasound conditions. For example, the energy introduced by the ultrasound field to induce cavitation effects can efficiently stimulate the decomposition of anions and / or additives in oxidizing solutions or their reaction with water molecules. Alternatively, ultrasound can be used to promote the homogenization of insoluble additive materials in oxidizing solutions, thereby simultaneously forming a composite interface structure composed of two or more insoluble elements or compounds.

[0014] This invention also provides a zinc anode with a composite interface structure, comprising a zinc substrate and a composite interface structure layer in situ constructed on the surface of the zinc substrate. The composite interface structure layer prepared by this invention can effectively isolate zinc from direct contact with the electrolyte, mitigate side reactions such as hydrogen release and corrosion, and simultaneously homogenize the interfacial electric field and zinc ion concentration field distribution, thereby effectively suppressing zinc dendrite growth, optimizing the interfacial stability of the zinc anode, and improving battery life and electrochemical performance.

[0015] Furthermore, the composite interface structure layer of the present invention can be a uniformly mixed structure, constructing a composite protective layer with highly uniform component distribution and no obvious phase separation on the surface of the zinc substrate. This structure typically contains one or more components, and the components are finely and uniformly dispersed and mixed at the micro or nanoscale, forming a continuous, dense, and isotropic interface layer. Alternatively, the composite interface structure layer of the present invention has a gradient distribution structure, where the composition or properties of the interface layer (such as zinc affinity, mechanical strength, and chemical stability) change continuously and controllably along a direction perpendicular to the zinc electrode surface (from the zinc substrate to the electrolyte). This partitioned synergistic design, through the smooth transition gradient characteristics, can systematically improve the deposition uniformity and mechanical stability of the composite interface layer, thereby enhancing the cycle life of the zinc anode. Attached Figure Description

[0016] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0017] Figure 1 This is a flowchart illustrating the preparation process of the zinc anode with a composite interface structure according to the present invention. Figure 2 This is a schematic diagram of the ultrasonic device of the present invention; Figure 3 The results are the long-cycle performance test results of the symmetrical cells assembled with zinc anodes obtained in Comparative Examples 1-2 and Example 1; Figure 4 The results show the long-cycle performance test results of the full cells assembled with zinc anodes obtained in Comparative Example 1 and Example 1. Detailed Implementation

[0018] This invention provides a method for the ultrasonic chemical preparation of a zinc anode with a composite interface structure, comprising the following steps: A zinc substrate is placed in an oxidizing solution and subjected to a redox reaction under ultrasonic conditions. During the redox reaction, a composite interface structure is constructed on the surface of the zinc substrate, resulting in a zinc anode with a composite interface structure. The oxidizing solution includes an electrolyte salt and a solvent.

[0019] In this invention, unless otherwise specified, all raw materials used in the preparation are commercially available products well known to those skilled in the art.

[0020] In this invention, the frequency of the ultrasound is 1~60kHz, and the power density is 1~300W / cm². 3 The duration is 1 minute to 8 hours, and the ultrasound mode includes a start-stop mode or an uninterrupted ultrasound mode; the start-stop mode can be ultrasound for 1 to 10 seconds and then stop for 1 to 10 seconds.

[0021] In this invention, the ultrasonic power density or ultrasonic frequency is directly related to the cavitation intensity, which affects the size and behavior of the cavitation bubbles. This invention limits the ultrasonic conditions to the above range. The resulting cavitation effect induces the decomposition of anions in the electrolyte salt on the one hand, and the microjets caused by cavitation also promote the formation of specific structures on the zinc anode surface on the other hand, ultimately achieving the optimal control effect under suitable parameters.

[0022] In this invention, the cation in the electrolyte salt is a metal ion that undergoes a displacement reaction with zinc; the metal ion includes one or more of the following: iron ion, copper ion, indium ion, tin ion, gallium ion, silver ion, bismuth ion, lead ion, nickel ion, palladium ion, and antimony ion.

[0023] In this invention, the anion is an anion that can react with water molecules or decompose itself; the anion includes BF4. - PF6 - SO4 2- S 2- CO3 2- NO3 - NO2 - F - and PO3F 2- One or more of the following.

[0024] In a specific embodiment of the present invention, an interfacial composite layer is prepared on the surface of a zinc substrate using indium tetrafluoroborate electrolyte via ultrasound. The specific reaction is as follows: the displacement reaction between indium ions and zinc ions occurs preferentially. After zinc ions and indium metal are displaced from the solution, fluoroborate ions in the solution decompose to generate boric acid and hydrofluoric acid, which then react with zinc ions to form zinc borate and zinc fluoride. The reaction formula is shown below: ; ; ; .

[0025] In this invention, the high-valence metal element in the electrolyte salt of the oxidizing solution has oxidizing properties, while the zinc matrix has reducing properties. Therefore, a spontaneous redox reaction is initiated between the two in the interface modification solution, transforming the high-valence metal ions into elemental metals. The anions, under the strong stimulation of ultrasonic cavitation, react with water molecules, transforming into anions that can combine with zinc ions or other cations in the solution to form insoluble compounds. Ultimately, a composite interface layer composed of two or more insoluble elements or compounds is formed on the zinc matrix surface. Without strong ultrasound, in the same short reaction time, the original oxidizing solution only undergoes a single redox reaction with zinc, forming an interface layer composed of elemental metals, without the additional effects of the components. When ultrasound is introduced, due to the acoustic cavitation effect and acoustic flow induced by the sound field within the solution, new chemical reaction pathways are activated, and the rate and uniformity of the reaction within the solution are improved, thus obtaining a composite interface structure.

[0026] In this invention, the oxidizing solution further includes an auxiliary agent; the auxiliary agent is an organic or inorganic material soluble in the solvent, or an organic or inorganic material insoluble in the solvent; in a specific embodiment, the auxiliary agent may be one or more of carbon materials, boron nitride, sodium phosphate, polyvinyl alcohol, sodium chloride, cellulose, and silicon dioxide; in a specific embodiment, it may be activated carbon powder, boron nitride, polyvinyl alcohol, or sodium phosphate.

[0027] This invention utilizes the physical or chemical properties of additives to form a layered structure on the surface of metallic zinc through chemical reaction or physical adhesion. These additives include substances with potential oxidizing properties or substances that can react on the zinc substrate surface under the induction of ultrasonic cavitation. In specific embodiments, boron nitride exhibits extremely high chemical stability over a wide voltage window (especially within the operating voltage range of zinc batteries), and is inert to acids, alkalis, and most electrolyte solutions. This effectively mitigates problems such as hydrogen evolution and corrosion in zinc batteries. Furthermore, while traditional coating methods result in poorly bonded BN protective layers that are prone to detachment, the BN-containing composite structure prepared in situ using ultrasonic chemistry is tightly bonded to metallic zinc and arranged in an orderly manner, greatly simplifying the process.

[0028] In this invention, the zinc matrix comprises pure zinc and / or zinc alloy; the pure zinc comprises zinc powder and / or zinc foil; the alloying elements in the zinc alloy include one or more of Sn, Bi, Ca, Au, Ag, Cu, B, C, Mg, In, Ga, Al, Mg, Ba, and Sb; and the zinc content in the zinc alloy is ≥50% by mass.

[0029] In this invention, the solvent includes one or more of water, alcohol solvent, ester solvent, ketone solvent, and dimethyl sulfoxide; the alcohol solvent may be one or more of methanol, ethanol, and propanol; the ester solvent may be one or more of ethyl acetate, methyl acetate, methyl propionate, methyl lactate, and dimethyl carbonate; and the ketone solvent may be one or more of acetone, methyl ketone, and methyl ethyl ketone.

[0030] In this invention, when the oxidizing solution includes an electrolyte salt and an auxiliary agent, the mass fraction of the auxiliary agent is 0.5-15%.

[0031] In this invention, the ultrasonic cavitation process further includes washing and drying the resulting product; the washing includes water washing and ethanol washing; this invention does not have any special limitations on the drying conditions.

[0032] The present invention also provides a zinc anode with a composite interface structure prepared by the ultrasonic chemical preparation method of the zinc anode described above, comprising a zinc substrate and a composite interface structure layer in situ constructed on the surface of the zinc substrate; The composite interface structure layer is composed of two or more elemental metals and / or compounds.

[0033] In this invention, the composite interface structure layer can be a uniformly mixed structure, which forms a composite protective layer on the surface of the zinc anode with highly uniform component distribution and no obvious phase separation. This structure usually contains one or more components, and the components are finely and uniformly dispersed and mixed at the micro or nanoscale to form a continuous, dense and isotropic interface layer.

[0034] Alternatively, the composite interface structure layer can be a gradient distribution structure: the composition or properties of the interface layer (such as zinc affinity, mechanical strength, and chemical stability) change continuously and controllably along a direction perpendicular to the electrode surface (from the zinc substrate to the electrolyte). Both structures of the present invention can systematically improve deposition uniformity and mechanical stability, thereby enhancing the cycle life of the zinc anode.

[0035] In a specific embodiment, taking the preparation of an interfacial composite structure on the surface of a zinc substrate by ultrasonic cavitation of indium tetrafluoroborate electrolyte as an example, the substitution reaction between indium ions and zinc ions occurs preferentially. Only after zinc ions are substituted out of the solution and fluoroborate ions in the solution decompose to generate boric acid and hydrofluoric acid will zinc borate and zinc fluoride be generated. The intermediate layer formed on the surface of metallic zinc is indium-rich metal, and the outer layer is a structure with a gradient distribution of zinc fluoride / zinc borate.

[0036] The present invention also provides the application of the zinc anode with the composite interface structure described in the above technical solution in zinc-based batteries.

[0037] In this invention, the zinc-based battery includes one of a zinc-ion battery, a zinc-air battery, and a zinc-based flow battery.

[0038] To further illustrate the present invention, the following detailed description, in conjunction with the accompanying drawings and embodiments, describes the zinc anode with a composite interface structure provided by the present invention, its ultrasonic chemical preparation method, and its application, but these descriptions should not be construed as limiting the scope of protection of the present invention.

[0039] Example 1 according to Figure 1 The flowchart shown illustrates the preparation of a zinc anode with a composite interface structure. The specific steps are as follows: The polished commercial zinc foil was placed in a 20% (w / w) indium tetrafluoroborate aqueous solution, while simultaneously immersing an ultrasonic amplitude transformer, using methods such as... Figure 2 An ultrasonic device is applied above (left side) with an ultrasonic frequency of 20 kHz and an ultrasonic power density of 20 W / cm². 3Turn on the ultrasonic power supply. The start / stop mode is 3 seconds of ultrasound followed by 3 seconds of stop. The ultrasound will automatically stop after 60 minutes. Remove the zinc foil and clean it thoroughly to obtain an indium-rich metal layer in the middle and an outer layer of In / Zn3(BO3)2 / ZnF. 3)2 Zinc anode with a gradient composite interface structure of / ZnF2.

[0040] Example 2 The polished commercial zinc foil was placed in a 20% (w / w) antimony sulfide aqueous solution, and 3% (w / w) sodium phosphate was added. The process was carried out as follows: Figure 2 An ultrasonic device is applied below (right side). The ultrasonic frequency is set to 20 kHz and the ultrasonic power density to 120 W / cm². 3 Turn on the ultrasonic power supply. The start-stop mode is 1 second of ultrasonication followed by 1 second of stopping. The ultrasonication will automatically stop after 3 hours. After removing the zinc foil and cleaning it, a zinc anode with a composite interface structure of Sb / ZnS / Zn3(PO3)2 is obtained.

[0041] Example 3 The polished commercial zinc foil was placed in a 15% (w / w) aqueous solution of palladium tetrafluoroborate tetraacetonitrile, while simultaneously immersing an ultrasonic amplitude transformer. The process was carried out using... Figure 2 An ultrasonic device is applied above the image. The ultrasonic frequency is set to 10 kHz, and the ultrasonic power density is 40 W / cm². 3 Turn on the ultrasonic power supply. The start-stop mode is 1 second of ultrasonication followed by 1 second of stopping. The ultrasonication will stop automatically after 5 minutes. After removing the zinc foil and cleaning it, a zinc anode with a composite interface structure of Pd / Zn3(BO3)2 / ZnF2 is obtained.

[0042] Example 4 The polished commercial zinc foil was placed in a 15% (w / w) aqueous solution of ferric phosphate, with 3% (w / w) sodium phosphate added as an additive. Simultaneously, an ultrasonic amplitude transformer was immersed in the solution, and the process was carried out as follows: Figure 2 An ultrasonic device is applied above the image shown. The ultrasonic frequency is set to 40 kHz, and the ultrasonic power density is 25 W / cm². 3 Turn on the ultrasonic power supply, set the start / stop mode to continuous ultrasonication, and automatically stop after 10 minutes of ultrasonication. Remove the zinc foil and clean it to obtain the zinc anode with the composite interface structure of Fe / Zn3(PO3)2 / ZnO.

[0043] Example 5 The polished commercial zinc foil was placed in a 15% (w / w) aqueous solution of copper nitrate, and 3% (w / w) of activated carbon powder was added. The process was carried out as follows: Figure 2 An ultrasonic device is applied below the image shown. The ultrasonic frequency is set to 60 kHz, and the ultrasonic power density is 100 W / cm². 3Turn on the ultrasonic power supply, set to continuous ultrasonic operation, and automatically stop after 3 hours of ultrasonication. Remove the zinc foil and clean it to obtain the zinc anode with a Cu / ZnO / C composite interface structure.

[0044] Example 6 The polished commercial zinc foil was placed in a 15% (w / w) aqueous solution of nickel nitrite, and 1% (w / w) of polyvinyl alcohol was added. The process was carried out as follows: Figure 2 An ultrasonic device is applied below the image shown. The ultrasonic frequency is set to 60 kHz, and the ultrasonic power density is 60 W / cm². 3 Turn on the ultrasonic power supply, set to continuous ultrasonic operation, and automatically stop after 3 hours of ultrasonication. Remove the zinc foil and clean it to obtain a zinc anode with a Ni / ZnO / PVA composite interface structure.

[0045] Example 7 The polished commercial zinc foil was placed in a 10% (w / w) aqueous solution of tin fluorophosphate, and then subjected to a process as follows: Figure 2 An ultrasonic device is applied below the image shown. The ultrasonic frequency is set to 20 kHz, and the ultrasonic power density is 50 W / cm². 3 Turn on the ultrasonic power supply, set the start / stop mode to continuous ultrasonication, and automatically stop after 30 minutes of ultrasonication. Remove the zinc foil and clean it to obtain a zinc anode with a composite interface structure of Sn / Zn3(PO3)2 / ZnF2.

[0046] Example 8 The polished commercial zinc foil was placed in a 10% gallium carbonate aqueous solution, and 5% boron nitride was added. Simultaneously, an ultrasonic amplitude transformer was immersed in the solution, and the process was carried out as follows: Figure 2 An ultrasonic device is applied above the device as shown. The ultrasonic frequency is set to 20 kHz, and the ultrasonic power is set to 150 W / cm². 3 Turn on the ultrasonic power supply. The start-stop mode is 1 second of ultrasonication followed by 1 second of stopping. The ultrasonication will stop automatically after 2 hours. After removing the zinc foil and cleaning it, a zinc anode with a Ga / ZnF2 / BN composite interface structure is obtained.

[0047] Example 9 The polished commercial zinc foil was placed in a 10% (w / w) aqueous solution of silver fluoride, and 5% (w / w) of sodium chloride was added. Simultaneously, an ultrasonic amplitude transformer was immersed in the solution, and the process was carried out as follows: Figure 2 An ultrasonic device is applied above the image. The ultrasonic frequency is set to 60 kHz, and the ultrasonic power density is 300 W / cm². 3 Turn on the ultrasonic power supply. The start-stop mode is 5 seconds of ultrasonication followed by 5 seconds of stop. The ultrasonication will automatically stop after 6 hours. After removing the zinc foil and cleaning it, a zinc anode with a composite interface structure of Ag / AgCl / ZnF2 is obtained.

[0048] Comparative Example 1 Commercial zinc foil after polishing.

[0049] Comparative Example 2 The polished commercial zinc foil was immersed in a 20% (w / w) aqueous solution of indium tetrafluoroborate for 60 minutes to obtain a zinc anode.

[0050] Test Example 1 The surfaces of the zinc anodes obtained in Example 1 and Comparative Example 2 were characterized by transmission electron microscopy. In Comparative Example 2, without ultrasonic cavitation, a severe and uneven interfacial reaction occurred on its surface, eventually forming an uneven porous structure. After ultrasonication was applied, thanks to the cavitation effect and acoustic flow, a uniform and dense corrugated structure was eventually formed.

[0051] The cross-section of the gradient composite interface structure of the zinc anode obtained in Example 1 was characterized by transmission electron microscopy. An indium-rich intermediate layer was formed on the surface of the zinc metal, and the outer layer was zinc fluoride / zinc borate, proving that the interface composite structure of the present invention is In / Zn3(BO 3)2 / ZnF2 gradient composite interface structure.

[0052] Test Example 2 The zinc anodes obtained in Comparative Examples 1-2 and Example 1 were assembled into Zn||Zn symmetric button cells, and the temperature was measured at 5 mA / cm². 2 Current density and 2 mAh / cm 2 Under capacity conditions, long-cycle performance tests were conducted on symmetrical batteries to measure the cycle life of different batteries.

[0053] Depend on Figure 3 The results show that at 5 mA / cm 2 Current density and 2 mAh / cm 2 Under capacity conditions, the commercial zinc foil of Comparative Example 1 short-circuited after 200 h, the zinc foil of Comparative Example 2 without ultrasonic cavitation short-circuited after 350 h, while the zinc foil of Example 1 with ultrasonic cavitation did not fail for more than 1800 h, proving that the composite interface structure prepared by the present invention has a protective effect on the zinc anode.

[0054] Activated carbon, Ketjen black, and PVDF (binder) were mixed evenly in a mass ratio of 8:1:1 to prepare a slurry. The slurry was uniformly coated onto a roller mill and compacted using a titanium mesh as the current collector. Iodine was then electrodeposited to obtain an iodine positive electrode sheet. Subsequently, zinc foil from Example 1 and Comparative Example 1 were used as negative electrodes and assembled with the above positive electrode sheet to obtain different full cells. The assembled full cells were subjected to charge-discharge tests at voltages of 0.2~1.8 V and currents of 3 A·g. -1 Under charging and discharging conditions, the capacity retention rate of different batteries was tested.

[0055] Depend on Figure 4 The results show that the zinc-iodine full cell assembled from zinc foil treated with ultrasonic chemical process in Example 1 remained stable within 3000 cycles, with a capacity maintained at 170 mAh / g and a capacity retention rate of nearly 83%. In contrast, the zinc-iodine full cell assembled from commercial zinc foil experienced significant capacity fluctuations after 500 cycles and completely short-circuited after 650 cycles. This fully demonstrates that the interfacial composite structure prepared in this invention has excellent performance in improving the cycle stability and efficiency of the battery.

[0056] In summary, the composite interface structure improves the stability, reversibility, and cycle life of zinc anodes. By suppressing dendrite growth, minimizing side reactions, and ensuring uniform zinc deposition, the composite interface-modified layer significantly enhances the prospects for high-performance, durable, and safe zinc-based energy storage systems.

[0057] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for ultrasonic chemical preparation of a zinc anode with a composite interface structure, characterized in that, Includes the following steps: A zinc substrate is placed in an oxidizing solution and subjected to a redox reaction under ultrasonic conditions. During the redox reaction, a composite interface structure is constructed on the surface of the zinc substrate, resulting in a zinc anode with a composite interface structure. The oxidizing solution includes an electrolyte salt and a solvent.

2. The ultrasonic chemical preparation method for zinc anode according to claim 1, characterized in that, The frequency of the ultrasound is 1~60kHz, and the power density is 1~300W / cm². 3 The duration is 1 minute to 8 hours; the ultrasound mode is either start-stop mode or continuous mode.

3. The ultrasonic chemical preparation method for zinc anode according to claim 1, characterized in that, The cations in the electrolyte salt are metal ions that can undergo a displacement reaction with zinc; the anions in the electrolyte salt are anions that can react with water molecules or decompose themselves.

4. The ultrasonic chemical preparation method for zinc anode according to claim 1, characterized in that, The oxidizing solution also includes additives.

5. The ultrasonic chemical preparation method for zinc anode according to claim 4, characterized in that, The additive is an organic or inorganic material that is soluble in the solvent; or an organic or inorganic material that is insoluble in the solvent.

6. The ultrasonic chemical preparation method for zinc anode according to claim 4, characterized in that, When the oxidizing solution includes an electrolyte salt and an auxiliary agent, the mass fraction of the auxiliary agent is 0.5-15%.

7. The zinc anode with a composite interface structure prepared by the ultrasonic chemical preparation method according to any one of claims 1 to 6, characterized in that, It includes a zinc substrate and a composite interface structure layer constructed in situ on the surface of the zinc substrate; The composite interface structure layer is composed of two or more elemental metals and / or compounds.

8. The application of the zinc anode with the composite interface structure as described in claim 7 in zinc-based batteries.

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