Ultrafine-grain zinc-manganese-iron ternary alloy negative electrode material of carbon battery and preparation method of ultrafine-grain zinc-manganese-iron ternary alloy negative electrode material

Abstract

The invention relates to an ultra-fine grain zinc-manganese-iron ternary alloy negative electrode material for a carbon battery, which is characterized by comprising the following components in percentage by weight: 0.15% < Fe < 3%, 0.3% < Mn < 1%, and the balance of Zn and inevitable impurities. And the grain size of the negative electrode material is submicron. The invention also discloses a preparation method of the negative electrode material. The obtained ternary alloy has the advantages of high corrosion resistance and excellent mechanical strength.

Description

Technical Field

[0001] This invention relates to a zinc-manganese-iron ternary alloy, and also to a method for preparing the zinc-manganese-iron ternary alloy, belonging to the field of zinc alloy technology. Background Technology

[0002] Traditional carbon-zinc zinc-manganese batteries use pure zinc as the negative electrode material, which is prone to electrochemical corrosion, leading to electrolyte leakage and capacity decay during long-term use. In NH4 or ZnCl2 electrolyte systems, the high chemical reactivity of pure zinc makes it susceptible to self-discharge reactions, reducing battery lifespan and potentially causing swelling or even rupture. Furthermore, uncontrolled growth of zinc dendrites can cause internal short circuits, severely impacting battery safety and reliability. These problems significantly hinder the practical application of high-performance carbon-zinc batteries.

[0003] Alloying modification is one of the effective ways to improve the performance of zinc anodes. By adding trace amounts of alloying elements to zinc, hydrogen evolution corrosion and dendrite growth can be significantly suppressed. Among them, zinc-bismuth alloys can reduce the self-discharge rate through the hydrogen evolution inhibition effect of bismuth; zinc-indium alloys can increase the hydrogen evolution overpotential on the electrode surface and enhance corrosion resistance. However, existing zinc alloy anodes still face problems such as insufficient mechanical strength, poor processing performance, and high cost, which limit their widespread application in commercial carbon-zinc batteries.

[0004] In conclusion, developing a zinc-based anode material that combines high corrosion resistance, excellent mechanical strength, and low cost to solve the problems of short lifespan and poor safety of traditional carbon batteries has significant engineering application value and market prospects. Summary of the Invention

[0005] The first technical problem to be solved by this invention is to provide a carbon-zinc battery ultrafine crystalline zinc-manganese-iron ternary alloy anode material with high corrosion resistance and excellent mechanical strength.

[0006] The second technical problem to be solved by the present invention is to provide a method for preparing a carbon-zinc battery ultrafine crystalline zinc-manganese-iron ternary alloy anode material with high corrosion resistance and excellent mechanical strength.

[0007] The technical solution adopted by the present invention to solve the first technical problem mentioned above is: a carbon-zinc battery ultrafine crystalline zinc-manganese-iron ternary alloy anode material, characterized in that the anode material is composed of the following components and their weight ratios: 0.15% < Fe < 3%, 0.3% < Mn < 1%, with the balance being Zn and unavoidable impurities; the grain size of the anode material is submicron.

[0008] Preferably, the negative electrode material consists of the following components and their weight ratios: 0.2%≤Fe≤2.4%, 0.4%≤Mn≤0.9%, with the balance being Zn and unavoidable impurities.

[0009] Preferably, the grain size of the negative electrode material is 0.1 μm to 0.95 μm.

[0010] The technical solution adopted by this invention to solve the second technical problem mentioned above is: a method for preparing an ultrafine crystalline zinc-manganese-iron ternary alloy anode material for carbon-zinc batteries, characterized by comprising the following steps:

[0011] ① Pure zinc, pure manganese and pure iron are mixed and smelted to obtain a cast zinc-manganese-iron alloy;

[0012] ② After homogenization treatment of the cast zinc-manganese-iron alloy, it is subjected to multiple rolling processes with a cumulative deformation of ≥80%, thereby obtaining an ultrafine-grained zinc-manganese-iron ternary alloy.

[0013] As a preferred option, the smelting conditions described in step ① are as follows: after smelting at 650-700℃ for 10-30 minutes, the mixture is poured into a mold at 600-650℃ and cooled to room temperature to obtain a zinc-manganese-iron ternary alloy ingot.

[0014] As a preferred embodiment, the homogenization treatment conditions in step ② are as follows: heating temperature is 320-380℃, and holding time is 5-6 hours.

[0015] Preferably, the rolling conditions in step ② are as follows: rolling speed is 0.5 to 2 m / min; the number of rolling passes is 15 to 25; and the deformation amount of each rolling pass is 10% to 30%.

[0016] Preferably, the cumulative deformation in step ② is 80% to 90%.

[0017] Compared with the prior art, the advantages of the present invention are as follows:

[0018] (1) Compared with pure zinc anode, the ultrafine crystalline zinc-manganese-iron alloy prepared in this invention has a submicron crystalline structure. The manganese content is less than 1 wt%, which plays a role in promoting grain refinement in the zinc alloy system and can improve the plasticity of the zinc alloy. The iron content is less than 3 wt%, which plays a role in improving the mechanical properties in the zinc alloy system.

[0019] (2) Compared with pure zinc anode, the ultrafine crystalline zinc-manganese-iron alloy anode prepared in this invention has significantly improved corrosion resistance by suppressing hydrogen evolution reaction and forming a dense passivation layer.

[0020] (3) Compared with pure zinc anodes, the ultrafine-grained zinc-manganese-iron alloy anode material prepared in this invention contains more Mn and Zn. 13The phase, acting as a uniform nucleation site, can guide the uniform deposition of zinc-manganese-iron alloy, inhibit the growth of zinc dendrites and the occurrence of side reactions, and greatly increase the lifespan of the zinc alloy anode.

[0021] (4) Compared with existing zinc alloy anodes, the anode material prepared by the present invention is designed to be completely lead-free.

[0022] (5) The preparation method of ultrafine zinc-manganese-iron alloy provided by the present invention can refine the zinc alloy grains to the submicron level by controlling the preparation process, and the preparation method is simple and easy to operate. Attached Figure Description

[0023] Figure 1 This is the grain size distribution of the Zn-0.4Mn-0.2Fe alloy prepared in Example 1;

[0024] Figure 2 This is a morphology diagram of the Zn-0.4Mn-0.2Fe alloy prepared in Example 1;

[0025] Figure 3 This is a morphology image of the Zn-0.6Mn-0.7Fe alloy prepared in Example 2;

[0026] Figure 4 The thickness measurement results are for the Zn-0.6Mn-0.7Fe alloy prepared in Example 2;

[0027] Figure 5 This is a morphology image of the Zn-0.7Mn-1.3Fe alloy prepared in Example 3;

[0028] Figure 6 This is a morphology diagram of the Zn-0.9Mn-2.4Fe alloy prepared in Example 4;

[0029] Figure 7 These are hardness measurement charts of the zinc alloys prepared in Examples 1, 2, 3, and 4;

[0030] Figure 8 These are Bode plots of the impedance modulus values ​​of the zinc alloys prepared in Examples 1, 2, 3, and 4.

[0031] Figure 9 These are the phase angle Bode diagrams of the zinc alloys prepared in Examples 1, 2, 3, and 4;

[0032] Figure 10 These are Nyquist diagrams of the zinc alloys prepared in Examples 1, 2, 3, and 4. Detailed Implementation

[0033] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0034] The ultrafine crystalline zinc-manganese-iron alloy provided in this embodiment of the invention comprises, by mass percentage, the following components: 0.15wt% < Fe < 3wt%, 0.3wt% < Mn < 1wt%, with the balance being Zn and unavoidable impurities; and the grain size of the ultrafine crystalline zinc-manganese-iron alloy is 0.1μm to 0.95μm, reaching the submicron level.

[0035] This invention optimizes the composition of an ultrafine-grained zinc-manganese-iron ternary alloy and combines it with a suitable preparation process to produce a ternary alloy with uniform and fine grains, thereby significantly improving the plasticity of the zinc alloy. The uniform ultrafine-grained structure of this alloy effectively suppresses localized corrosion of the zinc anode during high-current discharge of a primary battery, preventing perforation. This invention solves the problems of surface defects and unstable discharge performance existing in current carbon-zinc battery anode materials.

[0036] In the preparation method of this invention, manganese is added to the zinc alloy. Manganese improves the alloy's plasticity by refining the grains; however, excessive addition can lead to the precipitation of coarse second phases, which weakens the grain refining effect and reduces strength. Controlling the manganese content within the range of 0.3% to 1.0% can optimize surface quality while avoiding strength loss. For example, the Mn content can be 0.4%, 0.6%, 0.7%, or 0.9% by mass percentage, but is not limited thereto.

[0037] In zinc alloys, an appropriate amount of Fe can improve the alloy's hardness and strength through solid solution strengthening or the formation of a hard phase, thereby improving its compressive strength. However, excessively high iron content not only significantly reduces the alloy's plasticity, toughness, and ductility, leading to an increased tendency for processing cracks, but may also deteriorate the alloy's hot working and cold rolling properties, increasing its production difficulty. Therefore, the zinc-manganese-iron alloy of this invention strictly controls the Fe content within the range of 0.15wt% to 3wt%, primarily to enhance the alloy's compressive strength while ensuring its processing feasibility. As an example, the iron content in the zinc-manganese-iron alloy is 0.2%, 0.7%, 1.3%, or 2.4% by mass percentage, but is not limited to these.

[0038] In some embodiments of the present invention, in order to further enhance the synergistic effect among the components and to improve the surface quality and compressive strength of the zinc alloy, the ultrafine crystalline zinc-manganese-iron ternary alloy is composed of the following components by mass percentage: 0.2% ≤ Fe ≤ 2.4%, 0.4% ≤ Mn ≤ 0.9%, with the balance being Zn and unavoidable impurities.

[0039] In some embodiments of the present invention, the grain size of the ultrafine crystalline zinc-manganese-iron alloy is 0.1 μm to 0.95 μm.

[0040] The preparation method of ultrafine-grained zinc-manganese-iron alloy provided in this invention includes the following steps:

[0041] (1) Pure zinc, pure manganese and pure iron are mixed and smelted to obtain a cast zinc-manganese-iron alloy;

[0042] (2) After homogenizing the cast zinc-manganese-iron alloy obtained in step (1), it is subjected to multiple rolling processes to make the cumulative deformation of the cast zinc-manganese-iron alloy ≥80%, thereby obtaining an ultrafine-grained zinc-manganese-iron alloy negative electrode.

[0043] In some implementations, step (1) specifically includes: mixing pure zinc, pure manganese and pure iron, melting at 650-700°C for 10-30 minutes, pouring into a mold at 600-650°C, and obtaining a cast zinc-manganese-iron alloy ingot after cooling to room temperature.

[0044] In some specific implementation schemes, the raw materials of the ultrafine crystalline zinc-manganese-iron alloy are mixed according to the metering ratio, and the raw materials are melted at 650-700°C for 10-30 minutes, then poured into a mold at 600-650°C, and after cooling to room temperature, the cast zinc-manganese-iron alloy is obtained.

[0045] Based on the melting points of each component in the zinc-manganese-iron alloy, the smelting temperature is controlled between 650 and 700°C, and the smelting time is 10 to 30 minutes. The casting temperature is between 600 and 650°C. This allows the components to fully dissolve and reduces burn-off, resulting in the best-performing as-cast structure.

[0046] In some implementations, step (2) specifically includes: after removing the oxide scale from the cast zinc-manganese-iron alloy obtained in step (1), the cast zinc-manganese-iron alloy is subjected to homogenization treatment and multi-pass roll forming.

[0047] In some implementations, the ingot heating temperature during the homogenization process is 320–380°C, and the holding time is 5–6 hours.

[0048] In some implementations, the multi-pass roll forming process involves 15 to 25 passes.

[0049] In some implementations, the deformation per roll forming pass is 10% to 30%.

[0050] In some implementations, the cumulative deformation of the cast zinc-manganese-iron alloy is ≥80% through multiple roll forming processes.

[0051] In some embodiments, the rolling speed in the multi-pass roll forming is 0.5–2 m / min.

[0052] Appropriate rolling speed is beneficial to the rolling process and will also affect the microstructure of the material. The change in deformation per pass will significantly affect the grain size, thereby affecting the various properties of the material.

[0053] In some preferred embodiments, the as-cast zinc-manganese-iron alloy is subjected to homogenization treatment at a temperature of 340–360°C, with 20–25 extrusion passes, and the cumulative deformation of the as-cast zinc-manganese-iron alloy is ≥80%.

[0054] This invention provides an ultrafine-grained zinc-manganese-iron alloy prepared by the method described above.

[0055] This invention also provides the use of the aforementioned ultrafine crystalline zinc-manganese-iron alloy in the preparation of environmentally friendly carbon-zinc battery anode materials.

[0056] To make the objectives, technical solutions, and advantages of this invention clearer, the technical effects achievable by this invention will be further illustrated below with reference to embodiments. However, the selected embodiments are for illustrative purposes only and do not limit the scope of this invention.

[0057] Unless otherwise specified, all percentages used in the following examples are by mass, and the raw materials are pure zinc (99.99 wt.%), pure manganese (99.99 wt.%), and pure iron (99.99 wt.%).

[0058] Example 1: A method for preparing a Zn-0.4Mn-0.2Fe alloy negative electrode, specifically including the following steps:

[0059] In this embodiment, pure zinc, pure manganese, and pure iron powders are used as raw materials. These powders are mixed in a mass ratio of 99.4:0.4:0.2, and the mixture is smelted at 700°C for 30 minutes. The resulting ingot is then poured into a mold at 620°C and cooled to room temperature to obtain an alloy ingot of 50mm × 50mm × 200mm. The outer layer of the zinc-based alloy ingot is removed by turning. Subsequently, a 20mm × 20mm × 2mm thick sheet is prepared by precision wire cutting using a Φ0.18mm molybdenum wire at a cutting speed of 0.8mm / min. The obtained sheet is further homogenized (held in a muffle furnace at 350°C for 5 hours) and quenched to achieve a uniform composition throughout the ingot. The Zn-0.4Mn-0.2Fe alloy was then subjected to 20 passes of electric roller pressing (single reduction of 10-25%) to obtain a thin sheet of 0.10±0.02 mm. Finally, it underwent diamond polishing (3 μm, 0.2 MPa), alkaline degreasing, and acid pickling activation. The grain size of the Zn-0.4Mn-0.2Fe alloy was measured according to the standard GB / T6394-2017 "Method for Determination of Average Grain Size of Metals". The results are as follows: Figure 1As shown, its grain size is extremely fine, reaching the submicron level. The microstructure of this alloy was observed using a metallographic microscope, yielding... Figure 2 .

[0060] Example 2: A method for preparing a Zn-0.6Mn-0.7Fe alloy negative electrode, specifically including the following steps:

[0061] A systematic process was used to prepare Zn-0.6Mn-0.7Fe alloy anodes: In this embodiment, pure zinc, pure manganese, and pure iron powders were used as raw materials. These powders were mixed in a mass ratio of 98.7:0.6:0.7. The mixed raw materials were melted at 660℃ for 30 minutes and then poured into a mold at 620℃. After cooling to room temperature, alloy ingots of 50mm×50mm×200mm were obtained. The outer skin of the zinc-based alloy ingot was removed by turning. Then, precision wire cutting with Φ0.18mm molybdenum wire at a cutting speed of 0.8mm / min was performed to prepare 20mm×20mm×2mm thick sheets. The obtained thick sheets were further homogenized (held in a muffle furnace at 320℃ for 5 hours) and quenched to achieve a uniform composition throughout the ingot. The Zn-0.6Mn-0.7Fe alloy was then subjected to 15 passes of rolling (10-25% reduction per pass) using an electric roller mill to obtain a 0.10±0.02mm thin sheet. Finally, it underwent diamond polishing (3μm, 0.2MPa), alkaline degreasing, and acid pickling activation. The microstructure and thickness of the Zn-0.6Mn-0.7Fe alloy surface were observed using a metallographic microscope as shown below. Figure 3 and Figure 4 As shown

[0062] Example 3: A method for preparing a Zn-0.7Mn-1.3Fe alloy negative electrode, specifically including the following steps:

[0063] In this embodiment, pure zinc, pure manganese, and pure iron powders are used as raw materials. These powders are mixed in a mass ratio of 98.0:0.7:1.3. The mixture is then melted at 700°C for 30 minutes and poured into a mold at 620°C. After cooling to room temperature, an alloy ingot of 50mm × 50mm × 200mm is obtained. The outer layer of the zinc-manganese-iron alloy ingot is removed by turning. Then, using a Φ0.18mm molybdenum wire, precision wire cutting is performed at a cutting speed of 0.8mm / min to prepare a 20mm × 20mm × 2mm thick sheet. The obtained sheet is further homogenized (held in a muffle furnace at 350°C for 5 hours) and quenched to achieve a uniform composition throughout the ingot. The Zn-0.7Mn-1.3Fe alloy was then subjected to 25 passes of electric roller pressing (5-20% reduction per pass) to obtain a 0.10±0.02mm thin sheet. Finally, it underwent diamond polishing (3μm, 0.2MPa), alkaline degreasing, and acid pickling activation. The microstructure of the Zn-0.7Mn-1.3Fe alloy surface was analyzed using a metallographic microscope. Figure 5 As shown

[0064] Example 4: A method for preparing a Zn-0.9Mn-2.4Fe alloy negative electrode, specifically including the following steps:

[0065] In this embodiment, pure zinc, pure manganese, and pure iron powders are used as raw materials. These powders are mixed in a mass ratio of 96.7:0.9:2.4. The mixture is then melted at 700°C for 30 minutes and poured into a mold at 620°C. After cooling to room temperature, an alloy ingot of 50mm × 50mm × 200mm is obtained. The outer layer of the zinc-manganese-iron alloy ingot is removed by turning. Then, using a Φ0.18mm molybdenum wire, precision wire cutting is performed at a cutting speed of 0.8mm / min to prepare a 20mm × 20mm × 2mm thick sheet. The obtained sheet is further homogenized (held in a muffle furnace at 380°C for 5 hours) and quenched to achieve a uniform composition throughout the ingot. The Zn-0.9Mn-2.4Fe alloy was then subjected to 25 passes of electric roller pressing (5-20% reduction per pass) to obtain a 0.10±0.02mm thin sheet. Finally, it underwent diamond polishing (3μm, 0.2MPa), alkaline degreasing, and acid pickling activation. The microstructure of the Zn-0.9Mn-2.4Fe alloy surface was observed using a metallographic microscope. Figure 6 As shown

[0066] The zinc alloy prepared in the above embodiments was tested.

[0067] The hardness test involved the following steps: Before testing, the sample test surface was sequentially polished with 400#, 800#, 1200#, and 2000# metallographic sandpaper, and then polished to a mirror finish using 0.5μm diamond polishing paste before being securely fixed to the sample stage. A square pyramidal diamond indenter was used. Under a test load of 0.1 kgf, at least 10 different test points were randomly selected on each sample surface for indentation, with a holding time of 10 seconds. After unloading, the diagonal length of each indentation was precisely measured using the hardness tester's built-in optical microscope (measurement accuracy 0.001 mm). The equipment automatically calculated and displayed the Vickers hardness value (HV) for each test point. The final hardness value was the arithmetic mean of the multi-point measurements for each sample. The test results are as follows: Figure 7 As shown.

[0068] Electrochemical Testing: To characterize the corrosion resistance of the zinc-manganese-iron alloy anode, electrochemical tests were performed using an electrochemical workstation (GamryReference 3000) in a three-electrode system. The experimental setup consisted of zinc-manganese-iron alloy working electrodes (exposed area 1 cm²) prepared in Examples 1, 2, 3, and 4. 2The electrode consisted of a platinum auxiliary electrode and a saturated calomel reference electrode (SCE). The electrolyte was a 2M neutral ZnSO4 solution (pH = 6.8). Before testing, the electrode was placed in a constant temperature water bath at 25±0.5℃ for 30 minutes to achieve open-circuit potential stabilization. The test parameters were set as follows: a sinusoidal perturbation signal with an amplitude of 10mV was applied at the open-circuit potential, and the frequency scan range was 100kHz to 0.1Hz (logarithmic scan, 10 data points were collected every ten octaves). Open-circuit potential monitoring was performed for 30 minutes before testing, and formal measurement began after confirming that the potential fluctuation was less than ±2mV. All tests were conducted in a Faraday shielded box to reduce electromagnetic interference, and each sample was tested three times to ensure data reproducibility. The test results are as follows: Figure 8 , Figure 9 and Figure 10 As shown.

[0069] Figure 2 , Figure 3 , Figure 5 and Figure 6 The images show the morphology of the zinc-manganese-iron alloys prepared for the examples. It can be clearly observed from the images that the alloy samples with four different component ratios all exhibit a dense and uniform surface morphology, without obvious defects such as pores, cracks, or inclusions. In particular... Figure 2 and Figure 3 The Zn-0.4Mn-0.2Fe and Zn-0.6Mn-0.7Fe alloy samples shown exhibit the most uniform grain size distribution, with each alloying element showing a gradient distribution at the microscale, and no obvious compositional segregation. This uniform microstructure is beneficial for improving the alloy's electrical conductivity and corrosion resistance, fully meeting the technical requirements for uniformity and density of carbon-zinc battery anode materials.

[0070] Figure 4 The thickness measurement results of the zinc-manganese-iron alloy provided in Example 2; as shown Figure 4 As shown, the measured thickness of the alloy is 110.0 μm, which falls within the ideal thickness range for carbon-zinc battery anode materials. This thickness ensures good electron transfer, mechanical strength, and sufficient contact with the electrolyte within the battery, making it one of the key physical indicators for guaranteeing the overall electrochemical performance of the battery. Furthermore, it demonstrates the effectiveness and controllability of the preparation process employed in this invention.

[0071] Figure 7 The hardness measurement diagram of the zinc-manganese-iron alloy provided in the example; as shown. Figure 7 As shown, alloying significantly improves the hardness of the material, and the hardness increases with increasing iron content.

[0072] Figure 8 , Figure 9 and Figure 10Electrochemical impedance spectroscopy (EIS) of the zinc-manganese-iron alloy prepared for the example; as shown. Figure 10 As shown in the Nyquist plot, with the addition of appropriate amounts of Mn and Fe elements, the diameter of the capacitive arc in the mid-frequency region increases significantly, effectively suppressing corrosion. Figure 8 and Figure 9 The increase in low-frequency impedance and phase angle characteristics in the Bode plot further confirm this trend.

[0073] The performance test data shows that the above-described embodiments of the present invention achieve the following technical effects: By optimizing the composition of the zinc alloy anode material and combining it with a suitable preparation process, the prepared zinc alloy anode material has a uniform and fine microstructure and strong mechanical properties, significantly improving the surface quality and compressive strength of carbon-zinc battery anode materials, and solving the problems of surface defects and unstable discharge performance in the prior art. At the same time, the preparation method is simple and easy to industrialize. The prepared zinc alloy meets the requirements of carbon-zinc battery anode materials, with improved corrosion resistance and mechanical strength, and its performance indicators also meet the requirements for use in carbon-zinc battery anode materials, ensuring the application of ultrafine-grained zinc-manganese-iron alloy in the field of carbon-zinc battery anode materials.

[0074] Furthermore, the inventors of this case also conducted corresponding experiments using other alternative process conditions listed above, and the content to be verified is similar to that of the product in the embodiments. Therefore, the verification content of each embodiment will not be described one by one here, but only the embodiments are used as representatives to illustrate the advantages of this invention.

[0075] It should be understood that the above descriptions are only some embodiments of the present invention. It should be noted that those skilled in the art can make other modifications and improvements without departing from the inventive concept of the present invention, and these all fall within the protection scope of the present invention.

Claims

1. A carbon-zinc battery ultrafine crystalline zinc-manganese-iron ternary alloy anode material, characterized in that... The anode material is composed of the following components and their weight ratios: 0.15% < Fe < 3%, 0.3% < Mn < 1%, with the balance being Zn and unavoidable impurities; the grain size of the anode material is submicron.

2. The carbon-zinc battery ultrafine crystalline zinc-manganese-iron ternary alloy anode material according to claim 1, characterized in that... The anode material is composed of the following components and their weight ratios: 0.2%≤Fe≤2.4%, 0.4%≤Mn≤0.9%, with the balance being Zn and unavoidable impurities.

3. The environmentally friendly carbon-zinc battery ultrafine crystalline zinc-manganese-iron ternary alloy according to claim 1 or 2, characterized in that... The grain size of the negative electrode material is 0.1 μm to 0.95 μm.

4. A method for preparing the ultrafine crystalline zinc-manganese-iron ternary alloy anode material for carbon-zinc batteries according to any one of claims 1 to 3, characterized in that... Includes the following steps: ① Pure zinc, pure manganese and pure iron are mixed and smelted to obtain a cast zinc-manganese-iron alloy; ② After homogenization treatment of the cast zinc-manganese-iron alloy, it is subjected to multiple rolling processes with a cumulative deformation of ≥80%, thereby obtaining an ultrafine-grained zinc-manganese-iron ternary alloy.

5. The preparation method according to claim 4, characterized in that... The smelting conditions described in step ① are as follows: after smelting at 650-700℃ for 10-30 minutes, pour the molten zinc into a mold at 600-650℃, and obtain a zinc-manganese-iron ternary alloy ingot after cooling to room temperature.

6. The preparation method according to claim 4, characterized in that... The homogenization conditions described in step ② are as follows: heating temperature is 320-380℃, and holding time is 5-6 hours.

7. The preparation method according to claim 4, characterized in that... The rolling conditions described in step ② are as follows: rolling speed is 0.5 to 2 m / min; the number of rolling passes is 15 to 25; and the deformation amount of each rolling pass is 10% to 30%.

8. The preparation method according to claim 7, characterized in that... The cumulative deformation in step ② is 80% to 90%.

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