A zinc-ion battery negative electrode and its preparation method, and a zinc-ion battery.

Abstract

This invention provides a zinc-ion battery anode, its preparation method, and a zinc-ion battery. The zinc-ion battery anode includes a zinc foil with a zinc-affinity layer on its surface and a three-dimensional micropattern. The battery anode of this invention can induce a zinc ion concentration distribution through the imprinted three-dimensional micropattern and enhance zinc ion affinity using the zinc-affinity layer, achieving a unique microchannel-induced spatially selective deposition behavior. This not only homogenizes the zinc deposition process but also prevents short-circuit behavior caused by vertical dendrite growth, thereby obtaining a highly stable battery anode.

Description

Technical Field

[0001] This invention relates to the field of energy storage battery technology, and more specifically, to a zinc-ion battery negative electrode, its preparation method, and a zinc-ion battery. Background Technology

[0002] With the development of technology and the improvement of living standards, the demand for portable electronic products and electric vehicles is constantly growing, driving the development of energy storage devices with higher energy density and better stability. Rechargeable aqueous zinc-ion batteries (AZIBs) are widely considered a promising type of battery due to their advantages such as high safety, low redox potential, and large theoretical capacity.

[0003] However, the large-scale application of aqueous zinc-ion batteries is largely limited by the metal anode, such as the uncontrollable formation of zinc dendrites, hydrogen evolution reaction, and severe side reactions, which lead to poor cycle stability and even internal short circuits.

[0004] To optimize zinc deposition behavior, existing research has proposed modification strategies focusing on achieving uniform nucleation and good zinc ion distribution. For example, in-situ fabrication of zinc-loving thin films (such as zinc fluoride, zinc selenide, and zinc sulfide) on zinc metal anodes can slow zinc dendrite growth and accelerate reaction kinetics by lowering the nucleation energy barrier. However, aggregation and deposition still occur in areas with high zinc ion concentrations, and the zinc-loving thin film is destroyed due to volume expansion. Therefore, this technique is only effective at low current densities and limited capacities. Another approach is to construct three-dimensional porous zinc anodes, thereby reducing local current density and optimizing zinc ion distribution. Specifically, zinc-loving nanomaterials (such as silver, metal-organic framework materials ZIF-8, and graphene) can be deposited on three-dimensional conductive substrates (such as copper foam, MXene, and carbon foam) to provide a conductive cross-linking network and three-dimensional space for efficient zinc ion distribution. However, this method inevitably increases the total mass of the electrode and reduces the overall energy density of the device. Furthermore, the fabrication method requires an additional zinc electrodeposition step, which complicates the process and severely limits the large-scale production of batteries. In addition, the above-mentioned technical solutions are mostly focused on suppressing dendrite formation, but thermodynamic and kinetic studies have shown that the growth of zinc dendrites is inevitable.

[0005] Therefore, developing a metal anode that can effectively control dendrite distribution and avoid short-circuit risks is of great practical significance. Summary of the Invention

[0006] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a stable, high-capacity, and cyclic battery negative electrode under high current application conditions.

[0007] To achieve the above objectives, the first aspect of the present invention provides a zinc-ion battery negative electrode, comprising a zinc foil, wherein the surface of the zinc foil has a zinc-affinity layer, and the zinc foil has a three-dimensional micropattern.

[0008] Furthermore, the three-dimensional micro-pattern is selected from any of the following: arrayed triangles, arrayed circles, arrayed rectangles, and mosquito coil shapes.

[0009] Furthermore, the recess depth of the three-dimensional micropattern is 1-100 μm.

[0010] Furthermore, the zinc-loving material is selected from any one of the following: zinc selenide, silver, tin, zinc fluoride, and zinc sulfide.

[0011] The first aspect of this invention provides a method for preparing the above-mentioned zinc-ion battery negative electrode, comprising the following steps:

[0012] S1. Preparation of nanoimprint mold;

[0013] S2. A zinc-affinity material is generated on the zinc foil surface;

[0014] S3. Using a nanoimprinting mold, three-dimensional micro-patterns are imprinted on zinc foil with zinc affinity material to obtain a high-stability zinc-ion battery negative electrode.

[0015] Furthermore, in step S1, a programmable femtosecond laser technology is used to process the nanoimprint mold.

[0016] Furthermore, in step S2, a zinc-loving material is generated using surface deposition or displacement methods.

[0017] Furthermore, in step S3, the three-dimensional micro-pattern of the nanoimprint mold is imprinted onto a zinc foil with a zinc-affinity material using a rolling method.

[0018] A third aspect of the present invention provides a zinc-ion battery, comprising the above-described zinc-ion battery negative electrode, battery positive electrode, and electrolyte.

[0019] Furthermore, vertical graphene nanosheets of manganese dioxide are grown on the surface of the positive electrode of the battery, and the electrolyte is a mixed solution of zinc sulfate and manganese sulfate.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The battery anode of the present invention can induce the concentration distribution of zinc ions through imprinted three-dimensional micropatterns, and enhance the affinity of zinc ions by utilizing a zinc-loving layer, thereby realizing a unique microchannel-induced spatially selective deposition behavior. This not only homogenizes the zinc deposition process, but also prevents short-circuit behavior caused by vertical dendrite growth, thus obtaining a highly stable battery anode.

[0022] This invention directly uses zinc-loving zinc foil as the negative electrode, without any passivating material. It can quickly imprint three-dimensional micro-patterns using a simple imprinting technique. This preparation method is convenient, efficient, and suitable for large-scale production.

[0023] This invention utilizes programmable femtosecond laser technology to fabricate efficient and high-resolution nanoimprint molds, and the three-dimensional micro-patterns can be optimized according to the design. After imprinting zinc foil, a highly stable zinc-ion battery negative electrode with a well-arranged three-dimensional micro-pattern consistent with the mold structure can be obtained.

[0024] The zinc-ion battery of the present invention uses vertical graphene nanosheets with manganese dioxide grown on the surface as the positive electrode and zinc-loving foil with three-dimensional micropatterns as the negative electrode, which has many advantages such as high stability, high capacity and strong cycle performance. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the preparation process of the zinc-ion battery negative electrode in a specific embodiment of the present invention.

[0026] Figure 2 This is a schematic diagram illustrating the working principle of a zinc-ion battery in a specific embodiment of the present invention.

[0027] Figure 3 The images are scanning electron microscope (SEM) images of the negative electrode of the battery in Example 1 of this invention after zinc deposition at different current densities.

[0028] Figure 4 This is a scanning electron microscope image of the zinc foil and the negative electrode of the battery in Embodiment 2 of the present invention.

[0029] Figure 5 The figures show the current-voltage curves of the zinc-ion batteries of Embodiment 1 and Comparative Example 1 of the present invention.

[0030] Figure 6 The images show the electrochemical impedance spectroscopy of the zinc-ion batteries in Example 1 and Comparative Example 1 of this invention.

[0031] Figure 7 The graph shows the cycle performance test results of the zinc-ion batteries of Example 1 and Comparative Example 1 of this invention. Detailed Implementation

[0032] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be noted that the following embodiments are only used to illustrate the implementation methods and typical parameters of the present invention, and are not intended to limit the parameter range described in the present invention. Reasonable variations derived therefrom are still within the protection scope of the claims of the present invention.

[0033] It should be noted that the endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0034] The present invention discloses a zinc-ion battery negative electrode and its preparation method, such as... Figure 1 As shown, the preparation method of the zinc-ion battery negative electrode includes the following steps:

[0035] S1. Prepare a nanoimprint mold. Use programmable femtosecond laser technology to create a high-efficiency, high-resolution nanoimprint mold. In a specific embodiment, the three-dimensional micro-pattern of the mold is an array of triangles, circles, rectangles, mosquito coils, etc.

[0036] S2. A zinc-affinity layer is generated on the surface of the zinc foil using surface deposition or displacement methods. In specific embodiments, the zinc-affinity layer material is selected from zinc selenide, silver, tin, zinc fluoride, zinc sulfide, etc.

[0037] S3. The nano-imprinting mold uses a roller pressing method to imprint three-dimensional micro-patterns on zinc foil with zinc affinity material, so as to obtain a stable high-capacity zinc-ion battery negative electrode with a three-dimensional micro-pattern that is consistent with the mold structure and well arranged. In a specific embodiment, the recess depth of the three-dimensional micro-pattern is 1-100μm.

[0038] The present invention also discloses a zinc-ion battery, combined with Figure 2 As shown, the zinc-ion battery includes a negative electrode, a positive electrode, and an electrolyte. The negative electrode is a zinc-loving foil with a three-dimensional micropattern, the positive electrode is vertically grown graphene nanosheets of manganese dioxide, and the electrolyte is a mixed solution of zinc sulfate and manganese sulfate. Preferably, the electrolyte is a mixture of 2M zinc sulfate and 0.1M manganese sulfate solution.

[0039] The invention will be further described below with reference to specific embodiments.

[0040] Example 1

[0041] A 10*10cm piece was created using a femtosecond laser. 2 The nanoimprint mold has an array of triangular three-dimensional micropatterns with a depth of 20 μm.

[0042] A zinc-philic layer is generated by replacing a zinc-philic material on zinc foil, with metallic tin (Sn) being a typical example, because Sn can effectively accelerate reaction kinetics and promote uniform zinc nucleation. A one-step substitution method (Sn) is employed. 4+ +2Zn➝Sn+2Zn2+ Metallic tin is introduced onto the surface of zinc foil to obtain Sn@Zn.

[0043] Subsequently, Sn@Zn is imprinted using a nanoimprint mold to obtain a battery anode (Sn@Zn-IP) with a triangular surface structure.

[0044] The prepared negative electrode was assembled into a full cell with the positive electrode and electrolyte. Vertical graphene nanosheets of manganese dioxide were grown on the surface of the positive electrode. The electrolyte was a mixed solution of 2M zinc sulfate and 0.1M manganese sulfate.

[0045] Zinc is deposited on the negative electrode of the battery at different current densities. Figure 3 a is Sn@Zn-IP at 5mAh·cm -2 Scanning electron microscope image after volumetric Zn deposition. Figure 3 b represents Sn@Zn-IP at 10mAh·cm⁻¹ -2 Scanning electron microscope image after volumetric Zn deposition. Figure 3 c represents Sn@Zn-IP at 15mAh·cm⁻¹ -2 Scanning electron microscope image after volumetric Zn deposition. Figure 3 d represents Sn@Zn-IP at 20mAh·cm -2 Scanning electron microscope (SEM) image of zinc after volumetric deposition. The SEM image shows that the three-dimensional micropatterning guides the uniform deposition of zinc.

[0046] Example 2

[0047] A 10*10cm piece was created using a femtosecond laser. 2 The nanoimprint mold has an array of circular three-dimensional micropatterns with a depth of 30 μm.

[0048] A zinc-loving layer is prepared by replacing zinc-loving materials on zinc foil. Taking metallic silver (Ag) as a typical example, a one-step replacement method is used to introduce metallic silver onto the zinc foil surface to obtain Ag@Zn.

[0049] Subsequently, Ag@Zn is imprinted using a nanoimprint mold to obtain a Sn@Zn electrode (Ag@Zn-IP) with a circular surface structure. The surface structure of the zinc foil before imprinting is shown below. Figure 4 As shown in a and 4b, the surface structure of the negative electrode of the battery after imprinting is as follows: Figure 4 c, 4d are shown.

[0050] The prepared negative electrode was assembled into a full cell with the positive electrode and electrolyte. Vertical graphene nanosheets of manganese dioxide were grown on the surface of the positive electrode. The electrolyte was a mixed solution of 2M zinc sulfate and 0.1M manganese sulfate.

[0051] Example 2

[0052] A 10*10cm piece was created using a femtosecond laser. 2 The nanoimprint mold has an array of rectangular three-dimensional micropatterns with a depth of 10 μm.

[0053] A zinc-loving layer is prepared by replacing zinc-loving materials on zinc foil. Taking zinc selenide (ZnSe) as a typical example, zinc selenide is generated on the surface of zinc foil by surface deposition to obtain ZnSe@Zn.

[0054] Subsequently, ZnSe@Zn is imprinted using a nanoimprint mold to obtain a ZnSe@Zn electrode (ZnSe@Zn-IP) with a rectangular surface structure.

[0055] The prepared negative electrode was assembled into a full cell with the positive electrode and electrolyte. Vertical graphene nanosheets of manganese dioxide were grown on the surface of the positive electrode. The electrolyte was a mixed solution of 2M zinc sulfate and 0.1M manganese sulfate.

[0056] Example 3

[0057] A 10*10cm piece was created using a femtosecond laser. 2 The nanoimprint mold has a mosquito coil-shaped three-dimensional micro-pattern with a depth of 100μm.

[0058] A zinc-loving layer is prepared by replacing zinc-loving materials on zinc foil. Taking zinc sulfide (ZnS) as a typical example, zinc sulfide is generated on the surface of zinc foil by surface deposition to obtain ZnS@Zn.

[0059] Subsequently, ZnS@Zn is imprinted using a nanoimprint mold to obtain a ZnS@Zn electrode (ZnS@Zn-IP) with a mosquito coil-shaped structure on its surface.

[0060] The prepared negative electrode was assembled into a full cell with the positive electrode and electrolyte. Vertical graphene nanosheets of manganese dioxide were grown on the surface of the positive electrode. The electrolyte was a mixed solution of 2M zinc sulfate and 0.1M manganese sulfate.

[0061] Comparative Example 1

[0062] A complete battery was assembled using zinc foil as the negative electrode, vertical graphene nanosheets with manganese dioxide grown on the surface as the positive electrode, and a mixed solution of 2M zinc sulfate and 0.1M manganese sulfate as the electrolyte.

[0063] The current-voltage curves of the zinc-ion batteries in Example 1 and Comparative Example 1 were tested, and the results are as follows: Figure 5 As shown, the zinc-ion battery of Example 1 exhibits low voltage polarization, indicating its superior redox kinetics.

[0064] The electrochemical impedance of the zinc-ion batteries in Example 1 and Comparative Example 1 was tested, and the results are as follows: Figure 6As shown, the zinc-ion battery of Example 1 exhibits lower charge transfer resistance and faster ion migration behavior.

[0065] The cycle performance of the zinc-ion batteries in Example 1 and Comparative Example 1 was tested, and the results are as follows: Figure 7 As shown, after 500 cycles, the zinc-ion battery of Example 1 still retains 85.8% of its initial capacity, which is better than that of Comparative Example 1 (60.1%), further demonstrating that the zinc-ion battery of Example 1 has good negative electrode stability.

[0066] While the present invention has been disclosed above, it is not limited thereto. Any person skilled in the art can make various modifications and alterations without departing from the spirit and scope of the invention; therefore, the scope of protection of the present invention should be determined by the scope defined in the claims.

Claims

1. A zinc-ion battery anode, characterized in that, The zinc foil has a zincophilic layer on the surface, the material of the zincophilic layer is selected from any one of zinc selenide, silver, tin and zinc sulfide, and the zinc foil has a three-dimensional micro-pattern formed by imprinting, the three-dimensional micro-pattern is selected from any one of an array triangle, an array circle, an array rectangle and a mosquito coil shape, and the depth of the three-dimensional micro-pattern is 1-100 μm.

2. A method of preparing a zinc-ion battery anode as claimed in claim 1, characterized in that, The method comprises the following steps: S1, preparing a nano-imprint mold; S2, generating a zincophilic layer on the surface of the zinc foil; S3, imprinting a three-dimensional micro-pattern on the zinc foil with the zincophilic material by using the nano-imprint mold to obtain a high-stability zinc ion battery negative electrode.

3. The method of producing a zinc-ion battery anode according to claim 2, wherein, The nano-imprint mold is processed by using a program-controlled femtosecond laser technology in the step S1.

4. The method of producing a zinc-ion battery anode according to claim 2, wherein The zincophilic layer is generated by using a surface deposition or replacement method in the step S2.

5. The method of producing a zinc-ion battery anode according to claim 2, wherein The three-dimensional micro-pattern of the nano-imprint mold is imprinted on the zinc foil with the zincophilic material by using a roll pressing mode in the step S3.

6. A zinc-ion battery, characterized in that, The zinc ion battery negative electrode, a battery positive electrode and an electrolyte are provided.

7. The zinc-ion battery of claim 6, wherein, The battery positive electrode is a vertical graphene nanosheet with surface-grown manganese dioxide, and the electrolyte is a mixed solution of zinc sulfate and manganese sulfate.

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