A multi-component zinc alloy negative electrode obtained by using a low eutectic point and a preparation method and application thereof

Abstract

The application belongs to the technical field of zinc-based batteries, and particularly relates to a multi-component zinc alloy negative electrode obtained by using a low eutectic point and a preparation method and application thereof. The preparation method has the advantages of low alloying difficulty, trace addition and low-temperature preparation, and effectively solves the difficulty in alloy element selection and accurate addition by optimizing the addition process of elements. The application of the low eutectic principle to the preparation of the multi-component zinc alloy negative electrode can effectively reduce the burning loss of elements with high melting points, easy burning loss, large density and easy segregation, improve the alloy composition accuracy and distribution uniformity, effectively shorten the smelting time and reduce the energy consumption, and simultaneously add multiple elements to improve the alloy performance. The zinc alloy negative electrode prepared by the application can induce uniform zinc deposition, inhibit the dendrite growth on the zinc negative electrode surface and inhibit the side reactions such as hydrogen evolution corrosion; the battery assembled by using the zinc alloy negative electrode exhibits good cycle stability and significant safety performance, and has a wide application prospect.

Description

Technical Field

[0001] This invention belongs to the field of zinc-based battery anodes, specifically relating to a multi-component zinc alloy anode obtained using a low eutectic point, its preparation method, and its application. Background Technology

[0002] Aqueous zinc-based batteries using metallic zinc as the negative electrode have attracted widespread attention due to their enormous potential in energy storage. These characteristics stem 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 morphology growth, which may further cause short-circuit failure. Furthermore, corrosion and hydrogen evolution caused by the reactions between zinc and water molecules during chemical and electrochemical processes have become key bottlenecks hindering the commercial deployment of zinc-based batteries. Therefore, effectively suppressing dendrite growth, hydrogen evolution, and corrosion is a crucial scientific challenge in achieving reliable zinc-based batteries with high efficiency, high stability, and long cycle life.

[0003] Currently, various methods have been developed, including but not limited to interface protection layers, structural optimization design, electrolyte modification, and anode alloying. Among these, anode alloying has attracted widespread attention due to its ability to directly adjust the physicochemical properties of the zinc anode itself. Adding other metallic elements to the zinc anode can control the nucleation and growth behavior of zinc on the anode surface, construct an electrostatic shielding protective layer, and improve properties such as hydrogen evolution inhibition and corrosion resistance. However, current zinc anode alloying strategies generally employ metallic elements with melting points similar to zinc, or rely on the solid solution behavior of the metal in zinc in a non-molten state to achieve alloying. Such methods typically struggle to achieve precise control of the alloy composition, especially for metallic elements with significant differences in melting and boiling points from zinc. Thermodynamically, these elements are difficult to form a uniform and stable alloy phase with zinc, thus limiting the design and controllable preparation of multi-element alloy anode materials. Therefore, research and design of anode alloying materials and preparation processes are of great significance for the modification of zinc anodes in aqueous zinc-based batteries.

[0004] Against this backdrop, this invention innovatively introduces pre-alloying as the core driving force, targeting zinc alloy anodes containing elements that are difficult to directly alloy with zinc. It overcomes the limitations of selecting added metal elements in alloyed zinc anode strategies, improving addition efficiency and composition control precision. The pre-alloyed raw materials with designed compositions and melting paths, along with the target alloy material, are heated until all metals melt and mix uniformly. Cooling to room temperature then yields an applicable alloyed modified zinc alloy anode material. This provides a practical physicochemical method for solving the problem of directly adding certain elements during alloyed zinc anode modification. Summary of the Invention

[0005] To address the aforementioned deficiencies or improvement needs of existing technologies, this invention provides a multi-component zinc alloy anode obtained using a eutectic point and its preparation method. Through research and design of the elemental composition and metal melting path of the alloy anode, based on the eutectic phenomenon and the principle of element pre-alloying, the elemental composition of the pre-alloy is adjusted according to the phase diagram. By combining high-melting-point or low-melting-point metal elements with zinc matrix metal elements to form a pre-alloy, the overall melting point can be significantly reduced, or the alloy composition can be precisely controlled, increasing the dissolution rate and absorption rate of elements in the melt, and improving the uniformity of element distribution. This results in a zinc alloy anode containing elements difficult to add directly, which is impossible to achieve with traditional metal element addition processes. This improves the element selection range, compositional accuracy, and uniformity of the alloyed zinc anode, thereby improving the electrochemical cycle performance of zinc-based batteries. The preparation method of this invention is simple and convenient to operate and has good practical effects.

[0006] To achieve the above-mentioned objectives, according to one aspect of the present invention, a multi-component zinc alloy anode material obtained using a low eutectic point is provided. This material utilizes the low eutectic phenomenon of pre-alloying and the principle of element pre-alloying. The elemental composition of the pre-alloy is adjusted according to the phase diagram, and a metal melting path is designed to obtain a zinc alloy anode material containing elements difficult to directly add. This material is used for alloying zinc anode modification and to suppress dendrite growth. Specifically, the method for preparing the target zinc alloy anode material using pre-alloying involves placing the pre-alloyed raw material with the designed elemental composition in a heating container. The temperature is raised to a set temperature in a protective atmosphere, vacuum, or air to melt and mix the metal raw material uniformly. The mixture is then cooled to room temperature. The remaining material is then melted and mixed uniformly in a protective atmosphere, vacuum, or air according to the designed melting path, and then cooled to room temperature to obtain a zinc alloy anode material containing elements difficult to directly add.

[0007] In the above inventive concept, according to the conventional element addition conditions, the principle that the melting point of the added element is close to that of the matrix element should be followed. That is, when adding the required elements to the zinc melt, the difference in melting and boiling points between the added element and zinc shall be considered. Therefore, the added elements usually have a melting point close to that of zinc, and the melting temperature shall not exceed the boiling point of these elements; or the alloying is realized by relying on the solid solution behavior of the metal in zinc in the non-molten state. Due to the limitation of the melting and boiling points of these elements or their solid solubility in the zinc melt, there are great limitations in the selection of modification additive elements for the alloyed zinc negative electrode and the precision of element composition. When the pre-alloy is used to prepare the target zinc alloy, the overall melting temperature can be reduced, the smelting time can be shortened and the smelting temperature can be lowered due to the eutectic phenomenon of the pre-alloy and the principle of element pre-alloying; the target elements in the pre-alloy form a stable phase or solid solution, which are easier to dissolve and diffuse when added to the final melt, significantly reducing oxidation and volatilization loss; the composition of the pre-alloy is fixed, which can be added accurately through calculation, and is usually refined with high purity and less oxides, which is beneficial to realize the precise regulation of the final alloy composition and improve its purity. Finally, a zinc alloy negative electrode material containing elements that are difficult to add directly with uniform components and precise composition is obtained.

[0008] Further, the other elements in the pre-alloy raw material except zinc include Ti, Ni, Zr, Mn, Fe, V, Nb, Cr, Au, Ag, Cu, Sn, Bi, Ca, In, Ga, Al, Ce, Mg, Sb, Ge, B, Si, P, etc., and the forms include but are not limited to powder, particle, bulk, foil, etc. The mass content of metallic zinc in the finally prepared zinc alloy material is more than 50%. The element composition of the pre-alloy contains at least one element other than zinc. There are strict requirements between the melting and boiling points of each element it contains and the melting and boiling points of zinc. The melting point of zinc is T m0 =419.53 °C, and the boiling point is T b0 =906.9 °C; among the elements in the pre-alloy, the highest melting point is T1, the lowest melting point is T2, and the lowest boiling point is T3. Accordingly, the criteria are given: when the melting point T of the pre-alloy r0 <<T1, the prepared pre-alloy has a low eutectic point; only when T3>T1, T r0 <T b0 and T3>T m0 , the prepared alloy can be used as a pre-alloy.

[0009] Further, the smelting temperature in the smelting process depends on the melting and boiling points of the main and secondary components and the liquidus temperature of the alloy. The liquidus temperature of the pre-alloy is T LMA , that is, the minimum temperature required for the pre-alloy to melt completely; the liquidus temperature of the target zinc alloy is T LZA , that is, the minimum temperature required for the finally prepared zinc alloy to melt completely; the smelting temperature is T OP . The smelting process follows the following principles: (1) Ensure zinc is in a molten state: The smelting temperature must be higher than the melting point of pure zinc, i.e., T OP >T m0 ; (2) Ensure the pre-alloy is completely melted and dissolved: The melting temperature must be higher than or equal to the liquidus temperature of the pre-alloy, i.e., T OP ≥T LMA ; (3) Avoid violent volatilization and oxidation of metals: The smelting temperature must be significantly lower than the boiling point of pure zinc. If the temperature is too high, zinc will evaporate in large quantities (smoke, commonly known as "zinc burning"), and other low-boiling-point metals will also evaporate in large quantities, leading to unstable alloy composition, increased metal loss, and the generation of harmful fumes. High temperatures will also accelerate the oxidation of the melt surface, i.e., T OP < <T b0 ; (4) Ensure the final zinc alloy is liquid and has good fluidity: The melting temperature is usually slightly higher than the liquidus temperature of the final alloy to facilitate subsequent casting or processing, i.e., T OP ≥T LZA .

[0010] Based on the above principles, the following relationship formula can be obtained: max(T) m0 , T LMA , T LZA )≤T OP < <T b0 In actual production, to improve efficiency and ensure product quality, an optimized temperature range is usually selected. This temperature range should have the following characteristics: high enough to ensure rapid and uniform melting and dissolution of the pre-alloy; high enough to guarantee good fluidity of the final zinc alloy for easy casting; and low enough to minimize zinc volatilization loss and oxidation. Therefore, ideally, the liquidus temperature of the pre-alloy should be as close as possible to or lower than the casting temperature of the final zinc alloy (usually slightly higher than the target alloy liquidus temperature), and this casting temperature should be significantly lower than the boiling point of zinc. Thus: T m0 <T OP And strictly adhere to the above principles. The final relationship between the temperatures is max(T) LMA , T LZA )≤T OP ≤(T b0 -ΔT safety ), where ΔT safety For safety margin, it is generally 150 °C, to ensure that it is far from the boiling point of zinc and to prevent violent volatilization.

[0011] Furthermore, by utilizing the low eutectic point of pre-alloying and element pre-alloying methods, the zinc alloy anode obtained can add elements that are difficult to directly alloy with zinc to zinc or zinc alloys. This can solve the difficulties that some elements face when directly alloying with zinc, such as easy burn-off, large difference between their melting and boiling points and zinc, or easy segregation due to high density. This improves the addition efficiency, allows for precise control of composition, and ensures uniform alloying.

[0012] Furthermore, the protective atmosphere can be, but is not limited to, inert gases such as argon and nitrogen, as well as a single gas or mixture of gases that do not react with pure zinc or other pure metals. The techniques used for heating the metal include electromagnetic induction heating, arc melting, resistance heating, electron beam melting, laser melting, electrode heating, solar melting, salt bath melting, and other techniques applicable to heating metals. The set temperature is selected based on the alloy phase diagram; it can reach the melting point of only one metal or all metals. The heating container is one of a graphite crucible, a quartz glass tube, or other quartz glass containers. The graphite crucible must be pre-applied with a release agent or other additives to prevent carburization during preparation.

[0013] According to a second aspect of the present invention, a zinc-based battery including the zinc negative electrode as described above is also provided, which includes a zinc-ion battery, a zinc-air battery, and a zinc-based flow battery.

[0014] Furthermore, the pre-alloys required for preparing zinc alloy anode materials with uniform composition and precise composition containing elements difficult to add directly exist in the following two main functional forms: Form 1: Pre-alloying helps elements that are difficult to melt, easily oxidized, or poorly miscible with the main melt to enter the melt more efficiently and uniformly. Many pure metallic elements, especially trace elements with high melting points, large specific gravity differences, or strong chemical reactivity (such as titanium, boron, and rare earth elements), are prone to localized cooling, uneven melting, or even significant burn-off due to severe oxidation when directly added to the main melt (such as molten iron or aluminum). Pre-alloying dissolves these target elements in a carrier metal with a lower melting point and better compatibility with the main melt (such as aluminum-based, copper-based, or iron-based metals) to form a composite material with a moderate melting point and regular morphology. This not only lowers the effective melting point of the added element and accelerates its dissolution rate, avoiding thermal shock to the main melt, but also effectively removes the oxide film on the surface of the molten metal, improving wettability, thereby ensuring that the target element enters the melt efficiently and uniformly, and improving element recovery rate.

[0015] Form Two: Pre-alloying functions to precisely add elements: In modern alloy production, to impart specific properties to materials, it is often necessary to add trace amounts (such as a few parts per ten thousand or even a few parts per million) of microelements (e.g., grain refiners, modifiers, microalloying elements, etc.). Directly weighing and adding these high-concentration or pure microelements is not only difficult to operate and prone to large weighing errors, but also, due to their high reactivity or large density difference with the main melt, may lead to severe burn-off and uneven distribution. Pre-alloying pre-mixes the target element in a precisely controlled ratio (usually a few percent to tens of percent) into the base metal, thereby "diluting" the high-concentration, difficult-to-weigh pure element into a block or granular material that is easy to weigh and add. This greatly improves the weighing accuracy and recovery rate of added elements, ensuring that the content of the target element in the final alloy meets the strict process control requirements, ultimately guaranteeing the stability of product composition, the consistency of performance, and the reliability of mass production.

[0016] Compared with the prior art, the present invention has the following advantages and technical effects: This invention utilizes the eutectic phenomenon of pre-alloying and the principle of element pre-alloying to lower the overall melting temperature, solve the difficulty of adding certain elements, improve the accuracy and uniformity of composition, reduce burn-off, improve alloy performance, and reduce impurities, thereby preparing a zinc alloy anode material with uniform composition and accurate composition containing elements that are difficult to add directly. Firstly, the selection of alloying elements for modifying existing alloyed zinc anodes is limited by their melting and boiling points. However, by using pre-alloying to add the required elements, the problem of adding elements with high melting points, easy burn-off, and high density that are prone to segregation is effectively solved, thus preparing a zinc alloy anode material containing elements that are difficult to add directly.

[0017] Secondly, by designing the elemental composition and overall melting path of the pre-alloyed material, the compositional accuracy and distribution uniformity of the alloyed zinc anode can be improved. This enables low-temperature preparation of the zinc anode and the addition of trace amounts of alloying elements. The alloying elements are mainly used as functional additives or structural regulators to improve the deposition morphology of zinc, mitigate side reactions such as hydrogen release and corrosion, and suppress zinc dendrite growth, thereby enhancing the stability of the zinc anode and improving the battery's lifespan and electrochemical performance.

[0018] Thirdly, this invention utilizes pre-alloying to prepare zinc alloy anode materials with uniform composition and precise composition containing elements that are difficult to add directly, thus shortening the smelting process and reducing energy consumption. Compared with existing methods for adding modifying elements to alloyed zinc anodes, the preparation of alloyed zinc anodes using pre-alloying has a lower overall melting point and a faster melting rate, which can significantly shorten the alloy smelting time and cycle, improve smelting efficiency, improve alloy performance, and reduce production costs, thereby achieving the preparation of high-efficiency, precise, and controllable zinc alloy metal materials. Attached Figure Description

[0019] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention, and for those of ordinary skill in the art, other drawings can also be obtained based on these drawings without any creative effort.

[0020] Figure 1 is a preparation flow chart of the multi-component zinc alloy anode obtained by using the eutectic point of the present invention; Figure 2 is a comparison diagram of deposition / dissolution long-cycle performance test of Zn||Zn symmetric cells assembled with the multi-component zinc alloy anodes obtained by using the eutectic point in Comparative Example 1 and Example 5. Detailed Description of the Embodiments

[0021] In order to make the purposes, technical solutions and advantages of the present invention clearer, the present invention will be described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, and are not intended to limit the present invention. In addition, the technical features involved in the respective embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

[0022] In order to explain the content of the present invention in more detail, further description will be given below in conjunction with specific embodiments.

[0023] For the preparation method of the multi-component zinc alloy anode obtained by using the eutectic point, the experimental process is as Figure 1 shown.

[0024] Example 1 The melting point T of zinc m0 =419.53 °C (T2), and the boiling point T b0 =906.9 °C (T3); The melting point of pure aluminum (Al) is 660.4 °C (T1), and the boiling point is 2467 °C; The melting point T of the pre-alloy with the following atomic ratio r0 <<T1, that is, it has a low eutectic point; T3>T1, T r0 <T b0 and T3>T m0 , which can be used as a pre-alloy.

[0025] The preparation method of the multi-component zinc alloy anode obtained by using the eutectic point includes the following steps: 5 g of metal raw materials prepared by mixing pure Zn and pure Al at an atomic ratio of 88.7:11.3 are placed in a quartz glass tube, and under the protection of an argon atmosphere, all the raw materials are melted using a high-frequency electromagnetic induction heating device and then cooled to room temperature to obtain a material with a low melting point Tr0 pre-alloy; then all the pre-alloy is mixed with 45 g of pure Zn and placed in a crucible, under the protection of an argon atmosphere, the whole is heated from room temperature to 500 °C using a high-frequency electromagnetic induction heating device, and cooled to room temperature to obtain the target zinc alloy, after which the material is processed into a thin strip through a plastic deformation process and cut into the required zinc alloy negative electrode.

[0026] Example 2 The melting point T of zinc m0 =419.53 °C, and the boiling point T b0 =906.9 °C; The melting point of pure aluminum (Al) is 660.4 °C (T2), and the boiling point is 2467 °C (T3); The melting point of pure silicon (Si) is 1414 °C (T1), and the boiling point is 3265 °C; The melting point T of the pre-alloy with the following atomic ratio r0 <<T1, that is, it has a low eutectic point; T3>T1, T r0 <T b0 and T3>T m0 , which can be used as a pre-alloy.

[0027] A preparation method of a multi-component zinc alloy negative electrode obtained by using a low eutectic point, comprising the following steps: 5 g of raw material prepared by mixing pure Al and pure Si at an atomic ratio of 87.8:12.2 is placed in a quartz glass tube, under the protection of an argon atmosphere, all the raw materials are melted using a high-frequency electromagnetic induction heating device and then cooled to room temperature to obtain a pre-alloy with a low melting point T r0 ; then all the pre-alloy is mixed with 45 g of pure Zn and placed in a crucible, under the protection of an argon atmosphere, the whole is heated from room temperature to 600 °C using a high-frequency electromagnetic induction heating device, and cooled to room temperature to obtain the target zinc alloy, after which the material is processed into a thin strip through a plastic deformation process and cut into the required zinc alloy negative electrode.

[0028] Example 3 The melting point T of zinc m0 =419.53 °C, and the boiling point T b0 =906.9 °C; The melting point of pure copper (Cu) is 1083.4 °C (T1), and the boiling point is 2567 °C (T3); The melting point of phosphorus (P) is 590 °C (T2), and there is no general standard value for its boiling point under high pressure; The melting point T of the pre-alloy with the following atomic ratio r0 <<T1, that is, it has a low eutectic point; T3>T1, T r0 <T b0 and T3>T m0, which can be used as a pre-alloy.

[0029] A preparation method of multi-component zinc alloy negative electrode obtained by using a eutectic point, comprising the following steps: 3 g of raw materials prepared by mixing pure Cu and pure P at an atomic ratio of 84.2:15.8 are placed in a quartz glass tube, under the protection of an argon atmosphere, all the raw materials are melted using a high-frequency electromagnetic induction heating device and then cooled to room temperature to obtain a pre-alloy with a low melting point T r0 , then all the pre-alloy is mixed with 47 g of pure Zn and placed in a crucible, under the protection of an argon atmosphere, the whole is heated from room temperature to 750 °C using a high-frequency electromagnetic induction heating device, and cooled to room temperature to obtain the target zinc alloy, and then the material is processed into a thin strip through a plastic deformation process and cut into the required zinc alloy negative electrode.

[0030] Example 4 The melting point T of zinc m0 =419.53 °C, and the boiling point T b0 =906.9 °C; The melting point of pure aluminum (Al) is 660.4 °C (T2), and the boiling point is 2467 °C (T3); The melting point of pure copper (Cu) is 1083.4 °C, and the boiling point is 2567 °C; The melting point of pure silicon (Si) is 1414 °C (T1), and the boiling point is 3265 °C; The melting point T of the pre-alloy with the following atomic ratio r0 <<T1, that is, it has a low eutectic point; T3>T1, T r0 <T b0 and T3>T m0 , which can be used as a pre-alloy.

[0031] A preparation method of multi-component zinc alloy negative electrode obtained by using a eutectic point, comprising the following steps: 5 g of raw materials prepared by mixing pure Al, pure Cu and pure Si at an atomic ratio of 87.5:6.3:6.2 are placed in a quartz glass tube, under the protection of an argon atmosphere, all the raw materials are melted using a high-frequency electromagnetic induction heating device and then cooled to room temperature to obtain a pre-alloy with a low melting point T r0 , then all the pre-alloy is mixed with 45 g of pure Zn and placed in a crucible, under the protection of an argon atmosphere, the whole is heated from room temperature to 550 °C using a high-frequency electromagnetic induction heating device, and cooled to room temperature to obtain the target zinc alloy, and then the material is processed into a thin strip through a plastic deformation process and cut into the required zinc alloy negative electrode.

[0032] Example 5 The melting point T of zinc m0 =419.53 °C, and the boiling point T b0=906.9°C; The melting point of pure silver (Ag) is 961.78°C, and the boiling point is 2213°C; The melting point of pure copper (Cu) is 1083.4°C (T1), and the boiling point is 2567°C; The melting point of pure antimony (Sb) is 630.5°C (T2), and the boiling point is 1635°C (T3); The melting point T of the pre-alloy with the following atomic ratio r0 <<T1, that is, having a low eutectic point; T3>T1, T r0 <T b0 and T3>T m0 , which can be used as a pre-alloy.

[0033] The preparation method of the multi-component zinc alloy negative electrode obtained by utilizing the low eutectic point comprises the following steps: 5 g of metal raw materials prepared by mixing pure Ag, pure Cu and pure Sb according to an atomic ratio of 42.4:21.6:36.0 are placed in a quartz glass tube, under the protection of an argon atmosphere, all the raw materials are melted using a high-frequency electromagnetic induction heating device and then cooled to room temperature to obtain a pre-alloy with a low melting point T r0 , then all the pre-alloy is mixed with 45 g of pure Zn and placed in a crucible, under the protection of an argon atmosphere, the whole is heated from room temperature to 500°C using a high-frequency electromagnetic induction heating device, cooled to room temperature to obtain the target zinc alloy, and then the material is processed into a thin strip through a plastic deformation process and cut into the required zinc alloy negative electrode.

[0034] Example 6 The melting point T of zinc m0 =419.53°C, the boiling point T b0 =906.9°C; The melting point of pure silver (Ag) is 961.78°C, and the boiling point is 2213°C (T3); The melting point of pure copper (Cu) is 1083.4°C (T1), and the boiling point is 2567°C; The melting point of pure germanium (Ge) is 937.4°C (T2), and the boiling point is 2830°C; The melting point T of the pre-alloy with the following atomic ratio r0 <<T1, that is, having a low eutectic point; T3>T1, T r0 <T b0 and T3>T m0 , which can be used as a pre-alloy.

[0035] The preparation method of the multi-component zinc alloy negative electrode obtained by utilizing the low eutectic point comprises the following steps: 5 g of metal raw materials prepared by mixing pure Ag, pure Cu and pure Ge at an atomic ratio of 38.5:33.4:28.1 are placed in a quartz glass tube, and under the protection of an argon atmosphere, all the raw materials are melted using a high-frequency electromagnetic induction heating device and then cooled to room temperature to obtain a material with a low melting point T r0 master alloy, then all the master alloy is mixed with 45 g of pure Zn and placed in a crucible, under the protection of an argon atmosphere, the whole is heated from room temperature to 600 °C using a high-frequency electromagnetic induction heating device, and cooled to room temperature to obtain the target zinc alloy, after which the material is processed into a thin strip through a plastic deformation process and cut into the required zinc alloy negative electrode.

[0036] Example 7 The melting point T of zinc m0 =419.53 °C (T2), and the boiling point T b0 =906.9 °C (T3); Pure copper (Cu) has a melting point of 1083.4 °C (T1) and a boiling point of 2567 °C; Pure aluminum (Al) has a melting point of 660.4 °C and a boiling point of 2467 °C; The melting point T of the master alloy with the following atomic ratio r0 <<T1, that is, it has a low eutectic point; T3>T1, T r0 <T b0 and T3>T m0 , which can be used as a master alloy.

[0037] A preparation method of a multi-component zinc alloy negative electrode obtained by utilizing a low eutectic point comprises the following steps: 5 g of metal raw materials prepared by mixing pure Cu, pure Al and pure Zn at an atomic ratio of 31.1:65.9:3.0 are placed in a quartz glass tube, under the protection of an argon atmosphere, all the raw materials are melted using a high-frequency electromagnetic induction heating device and then cooled to room temperature to obtain a master alloy with a low melting point T r0 , then all the master alloy is mixed with 45 g of pure Zn and placed in a crucible, under the protection of an argon atmosphere, the whole is heated from room temperature to 700 °C using a high-frequency electromagnetic induction heating device, and cooled to room temperature to obtain the target zinc alloy, after which the material is processed into a thin strip through a plastic deformation process and cut into the required zinc alloy negative electrode.

[0038] Comparative Example 1 An untreated commercial zinc foil is used as the comparative example.

[0039] The zinc alloy negative electrodes obtained in Comparative Example 1 and Example 5 are assembled into a Zn||Zn symmetric coin cell, at a current density of 2 mA / cm 2 and a capacity of 1 mAh / cm 2At a given capacity, long-cycle performance tests were conducted on symmetrical batteries to test the cycle life of different batteries.

[0040] Figure 2 These are the results of long-cycle performance tests for symmetrical cells. At 2 mA / cm²... -2 Current density and 1 mAh / cm -2 The battery assembled with bare zinc at the specified capacity short-circuited after 40 hours, while the battery assembled with a zinc-silver-copper-antimony alloy anode obtained with a low eutectic point operated for more than 130 hours without failure, proving that the zinc alloy material prepared using the low eutectic point has good stability and cycle life.

[0041] This invention utilizes a zinc alloy anode material prepared with a low eutectic point, exhibiting excellent stability, reversibility, and cycle life. By suppressing side reactions such as dendrite growth, hydrogen evolution, and corrosion, and inducing uniform zinc deposition, this invention's method for preparing zinc alloy anodes using a low eutectic point significantly improves the performance of zinc alloy anodes, including long-term stability and safety, thus expanding the prospects for zinc-based energy storage systems.

[0042] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, not all embodiments. People can obtain other embodiments based on the present invention without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing a multi-component zinc alloy negative electrode using a low eutectic point, characterized in that, Includes the following steps: S1. Mix pre-alloy raw materials with designed element types and ratios, and perform smelting in a protective atmosphere or vacuum to obtain a pre-alloy; the melting points and boiling points of the elements other than zinc contained in the pre-alloy shall meet the following requirements with respect to the melting point and boiling point of zinc: the melting point of zinc T m0 =419.53°C, boiling point T b0 =906.9°C; the maximum melting point of the elements other than zinc in the pre-alloy is T1, the minimum melting point is T2, and the minimum boiling point is T3; when the melting point T of the pre-alloy r0 <<T1, the prepared pre-alloy has a low eutectic point; only when T3>T1, T r0 <T b0 and T3>T m0 , the prepared alloy can be used as a pre-alloy; S2. Mix the pre-alloy with zinc and melt it in a protective atmosphere or vacuum to obtain a zinc alloy material. S3. The zinc alloy material is subjected to plastic deformation treatment to obtain the zinc alloy negative electrode.

2. The preparation method according to claim 1, characterized in that, The pre-alloyed raw material in step S1 contains at least one element other than zinc. The elemental composition of the pre-alloyed raw material includes two or more of the following: Ti, Ni, Zr, Mn, Fe, V, Nb, Cr, Au, Ag, Cu, Sn, Bi, Ca, In, Ga, Al, Ce, Mg, Sb, Ge, B, Si, P, and Zn.

3. The preparation method according to claim 1 or 2, characterized in that, The pre-alloyed raw materials may be in the form of powder, granules, blocks, or foil.

4. The preparation method according to claim 1, characterized in that, The smelting process described in steps S1 and S2 involves a smelting temperature that depends on the melting and boiling points of zinc, the elements in the pre-alloy, and the liquidus temperature of the alloy; the liquidus temperature of the pre-alloy is T. LMA This refers to the minimum temperature required for the pre-alloy to completely melt; the liquidus temperature of the target zinc alloy is T. LZA This refers to the minimum temperature required for the final zinc alloy to completely melt; the melting temperature is T. OP The smelting process must meet the following principles: (1) Ensure zinc is in a molten state; (2) Ensure the pre-alloy is completely melted and dissolved; (3) Avoid violent volatilization and oxidation of the metal; (4) Ensure the final zinc alloy is liquid and has good fluidity; Based on the above principles, the relationship between the temperatures can be obtained as max(T LMA , T LZA )≤T OP ≤(T b0 -ΔT safety ), where ΔT safety For safety margin, 150 °C is used to ensure that the temperature is far from the boiling point of zinc and to prevent its violent volatilization.

5. The preparation method according to claim 1, characterized in that, The zinc alloy material contains more than 50% zinc by mass.

6. The preparation method according to claim 1, characterized in that, The protective atmosphere includes, but is not limited to, argon, nitrogen, and inert gases, as well as single or mixed gases that do not react with pure zinc or other elements other than zinc; the heating technology used to raise the temperature to the melting temperature includes electromagnetic induction heating, electric arc melting, resistance heating, electron beam melting, laser melting, or electrode heating technology; the set temperature is selected according to the alloy phase diagram or the melting and boiling points of the metal; the container required for melting is one of graphite crucibles, quartz glass tubes, and other quartz glass containers.

7. The zinc alloy negative electrode obtained by the preparation method according to any one of claims 1 to 6.

8. The application of the zinc alloy negative electrode of claim 7 in a zinc-based battery, wherein the zinc-based battery includes a zinc-ion battery, a zinc-air battery, or a zinc-based flow battery, and the negative electrode of the zinc-based battery is the zinc alloy negative electrode of claim 7.

9. A battery using the zinc alloy negative electrode as described in claim 7; the battery comprising a lithium-ion battery, a sodium-ion battery, a magnesium-ion battery, an aluminum-ion battery, or a battery without a negative electrode material.

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