KR20210111708A - Fabrication Method of Anode for Zinc-Ion Battery and Anode for Zinc-Ion Battery manufactured Therefrom and Aqueous Zinc-Ion Battery comprising the Same - Google Patents

Abstract

The present invention relates to a method for manufacturing an anode for a zinc-ion battery using a wet chemistry process, and more specifically, to a method for manufacturing an anode for a zinc-ion battery, comprising the steps of: a) preparing a zinc oxide-zinc (ZnO/Zn) composite by oxidizing one surface of a zinc substrate; and b) immersing the zinc oxide-zinc (ZnO/Zn) composite in an aqueous precursor solution and drying the same to obtain a porous metal-organic framework (Zn-MOF) containing zinc on the zinc substrate. According to the present invention, the anode for a zinc-ion battery comprising a hydrophilic and porous metal-organic framework layer can be provided so as to provide an aqueous zinc-ion battery with improved cycle life and safety.

Description

A method of manufacturing an anode electrode for a zinc-ion battery, an anode electrode for a zinc-ion battery manufactured thereby, and an aqueous zinc-ion battery comprising the same Zinc-Ion Battery comprising the Same}

The present invention relates to a method for manufacturing an anode electrode for a zinc-ion battery, an anode electrode for a zinc-ion battery manufactured by the same, and an aqueous zinc-ion battery comprising the same, in detail, zinc plating-stripping process It relates to a method for manufacturing an anode electrode for a zinc-ion battery having high efficiency electrochemical performance and improved lifespan and stability, an anode electrode for a zinc-ion battery manufactured thereby, and an aqueous zinc-ion battery including the same.

Recently, along with rapid technological growth in relation to the production of renewable energy, energy demand for automobiles, portable electronic devices, etc. is increasing, and the demand for a sustainable energy storage system having high efficiency for smart buildings is also increasing. In order to satisfy these demands, it is necessary to develop a new renewable energy storage device that is environmentally friendly, has stability, and has a high energy density that can be economically manufactured.

As one of the devices that can satisfy the above requirements, it is a zinc-based energy storage system with high theoretical capacity, low reduction potential (-0.764 V), excellent stability in aqueous electrolytes, eco-friendliness, safety and ease of processing. There is a growing interest in

Despite these many advantages, in the case of a zinc battery system, dendrite formation due to non-uniform charge distribution in the zinc electrode and side effects such as hydrogen generation or zinc corrosion during plating-stripping Due to this, there are significant restrictions on the efficiency and lifespan of the zinc battery system, which limits practical application.

In order to solve the problem of short circuit caused by such zinc dendrites, Japanese Patent JP 6677860 B2 provides an anode structure in which the entire anode active material layer is wrapped with a nonwoven fabric and a layered double oxide (LDH) separator, and have.

However, the effect is insignificant, the manufacturing process is complicated as separate sealing between different materials is required, and the production cost is increased, etc. All satisfactory results were not obtained.

Therefore, in the zinc battery system, it is possible to solve the problem of short circuit caused by zinc dendrite occurring in the zinc electrode, prevent side effects such as zinc corrosion, and at the same time, the manufacturing process is simple, and it is possible to respond to the recent demand. The need for the development of a large-scale zinc electrode is emerging.

Japanese Patent JP 6677860 B2

An object of the present invention is to provide a method for manufacturing an anode electrode for a zinc-ion battery that can be manufactured by a simple manufacturing process and extending to a large-scale through a wet chemistry method.

Another object of the present invention is to provide an anode electrode for a zinc-ion battery having a high-efficiency plating-stripping performance.

Another object of the present invention is to provide an anode electrode for a zinc-ion battery having excellent cycle life and safety.

Another object of the present invention is to provide an aqueous zinc-ion battery comprising an anode electrode for a zinc-ion battery.

A method for manufacturing an anode electrode for a zinc-ion battery according to an aspect of the present invention comprises: a) oxidizing one surface of a zinc substrate to prepare a zinc oxide-zinc (ZnO/Zn) composite; and b) immersing the zinc oxide-zinc (ZnO/Zn) composite in an aqueous precursor solution and drying it to prepare a zinc-containing porous metal-organic framework (Zn-MOF) on a zinc substrate including;

In the method for manufacturing an anode electrode for a zinc-ion battery according to an embodiment of the present invention, the metal-organic framework is a monolithic layer formed by directly growing on the surface of a zinc oxide-zinc (ZnO/Zn) composite. layer) can be

In the method for manufacturing an anode electrode for a zinc-ion battery according to an embodiment of the present invention, the metal-organic framework may be a zeolitic imidazolate framework (ZIF).

In the method of manufacturing an anode electrode for a zinc-ion battery according to an embodiment of the present invention, the zeolite-type imidazolate structure may be ZIF-8.

In the method of manufacturing an anode electrode for a zinc-ion battery according to an embodiment of the present invention, the aqueous precursor solution may include an imidazole-based precursor.

In the method of manufacturing an anode electrode for a zinc-ion battery according to an embodiment of the present invention, the porous metal-organic framework may include micropores.

In an embodiment of the present invention, the method for manufacturing an anode electrode for a zinc-ion battery may further include a step of thermal decomposition after step b).

In one embodiment of the present invention, the heating rate (heating rate) during thermal decomposition may be 50 to 90 ℃ / s.

In one embodiment of the present invention, the thermal decomposition may be performed in a temperature range of 500 to 900 ℃.

In one embodiment of the present invention, pyrolysis may be performed for 1 to 10 minutes.

According to another aspect of the present invention, a zinc metal substrate; and a porous metal-organic framework layer disposed on a zinc metal substrate and comprising zinc, wherein the surface of the porous metal-organic framework layer is hydrophilic.

According to an embodiment of the present invention, the hydrophilic metal-organic framework layer may satisfy Equation 1 below.

(Equation 1)

θ ₁ = xθ ₂ (1.1 ≤ x ≤ 1.4)

In Equation 1, θ ₁ is the water contact angle of the zinc metal substrate, and θ ₂ is the water contact angle of the metal-organic framework layer.

According to an embodiment of the present invention, the metal-organic framework may be a zeolitic imidazolate framework (ZIF).

According to an embodiment of the present invention, the zeolite-type imidazolate structure may be ZIF-8.

According to another aspect of the present invention, a zinc metal substrate; And located on the zinc metal substrate, nitrogen-doped porous carbon layer; provides a zinc-ion battery anode electrode comprising a.

According to an embodiment of the present invention, the porous carbon layer doped with nitrogen may be prepared by thermally decomposing a metal-organic framework.

According to an embodiment of the present invention, the porous carbon layer doped with nitrogen may contain 5 to 25 atomic% nitrogen.

According to an embodiment of the present invention, the porous carbon layer doped with nitrogen may satisfy Equation 2 below.

(Equation 2)

θ ₁ = xθ ₂ (1.5 ≤ x ≤ 4.0)

In Equation 2, θ ₁ is the water contact angle of the zinc metal substrate, and θ ₂ is the water contact angle of the porous carbon layer doped with nitrogen.

According to an embodiment of the present invention, the porous carbon layer may include macropores.

The present invention provides a rechargeable water-based zinc-ion battery comprising the above-described anode electrode for a zinc-ion battery.

The manufacturing method of the anode electrode for a zinc-ion battery according to the present invention is a wet chemistry process, the manufacturing process is simple, and a large-scale zinc-ion battery anode electrode can be manufactured.

The anode electrode for a zinc-ion battery according to the present invention has a hydrophilic surface and includes a porous metal-organic framework layer to effectively inhibit dendrite formation, thereby improving the cycle life and safety of an aqueous zinc-ion battery. have.

1A, 1B, and 1C are diagrams showing optical photographs of Comparative Examples 1, 2 and 1 in large-scale.
Figure 2a shows a schematic diagram in which Comparative Example 2, Examples 1, and Examples 2 to 4 are sequentially prepared from Comparative Example 1.
2b1, 2b2, 2b3, 2b4, 2b5 and 2b6 show SEM images of Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3 and Example 4, respectively; 2C is a diagram showing an optical photograph of each sample.
2d1, 2d2, and 2d3 are diagrams showing cross-sectional SEM images and energy dispersive X-ray spectroscopy (EDS) element mapping images of Comparative Example 2, Example 1, and Example 3, respectively.
3A is a diagram illustrating the measured XRD patterns of Comparative Examples and Examples, and FIG. 3B is a diagram simulating the XRD pattern of ZIF-8.
4 is a view showing Raman spectra of Comparative Examples and Examples.
5 is a diagram illustrating XPS survey spectra of Comparative Examples and Examples.
6 is a diagram showing high-resolution spectra of the C1s peak observed in Examples 1 to 4;
7 is a diagram showing high-resolution spectra of the N1s peak observed in Examples 1 to 4;
8 is a view showing the water contact angles of Comparative Examples and Examples.
9A is a diagram illustrating a cyclic voltammetry (CV) profile in a two-electrode experiment, and FIG. 9B is a diagram illustrating a CV profile in a three-electrode experiment.
Figure 9c is a schematic diagram of the modified anode electrode, Figure 9d shows the SEM image of the modified anode electrode, Figure 9e shows the SEM image of the modified anode electrode after 300 cycles.
10A and 10B are diagrams showing the cycle stability of each anode electrode in a current density ranging from 1 to 10 mA/cm ^{2 and a capacity ranging from 1 to 10 mAh/cm 2 .}
11A, 11B, 11C, 11D, 11E and 11F are galvanized-galvanized cells of symmetrical cells composed of Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3 and Example 4, respectively; A diagram showing an SEM image of each anode electrode measured after a cycle of plating-stripping.
Figure 12a is a view showing the CV profile of each water-based ZIB prepared, Figures 12b, 12c and 12d are the cycle performance of each water-based ZIB at each current rate (C-rate) 0.1, 0.5 and 1C the drawing shown.

Unless otherwise defined in technical terms and scientific terms used in this specification, those of ordinary skill in the art to which this invention belongs have the meanings commonly understood, and in the following description and accompanying drawings, the subject matter of the present invention Descriptions of known functions and configurations that may unnecessarily obscure will be omitted.

Also, the singular form used herein may be intended to include the plural form as well, unless the context specifically dictates otherwise.

In addition, the numerical range used herein includes the lower limit and upper limit and all values within the range, increments logically derived from the form and width of the defined range, all values defined therein, and the upper limit of the numerical range defined in different forms. and all possible combinations of lower limits. Unless otherwise defined in the specification of the present invention, values outside the numerical range that may occur due to experimental errors or rounding of values are also included in the defined numerical range.

As used herein, the term 'comprising' is an open-ended description having an equivalent meaning to expressions such as 'comprising', 'containing', 'having' or 'characterized', and elements not listed further; Materials or processes are not excluded.

In addition, as used herein, the term 'substantially' means that other elements, materials, or processes not listed together with the specified element, material or process are unacceptable for at least one basic and novel technical idea of the invention. It means that it can be present in an amount or degree that does not significantly affect it.

A method for manufacturing an anode electrode for a zinc-ion battery according to an aspect of the present invention comprises: a) oxidizing one surface of a zinc substrate to prepare a zinc oxide-zinc (ZnO/Zn) composite; and b) immersing the zinc oxide-zinc (ZnO/Zn) composite in an aqueous precursor solution and drying it to form a porous metal-organic framework (Zn-MOF) containing zinc on a zinc substrate. manufacturing step;

In the present invention, a zinc oxide-zinc (ZnO/Zn) composite in which zinc oxide is formed on one surface of a zinc substrate by oxidizing one surface of a zinc substrate is prepared, and then the composite is immersed in an aqueous precursor solution, followed by drying wet chemistry Provided is a method of manufacturing an anode electrode for a zinc-ion battery in which a porous metal-organic framework including zinc on a zinc substrate is prepared through a (wet chemistry) process.

At this time, the zinc oxide formed on one surface of the zinc substrate in the zinc oxide-zinc (ZnO/Zn) composite may have a higher reactivity compared to the natural oxide film of pure zinc in the process of forming the metal-organic framework, so the porosity to be performed later It is advantageous for the preparation of metal-organic frameworks. As such, the present invention has the advantage of being able to form a dense porous metal-organic framework on a zinc substrate without the use of a separate sealing process or adhesive unlike the prior art, and through this, It has the advantage of being able to solve the problem that the battery is short-circuited by the due to the short circuit and prevent side effects such as zinc corrosion.

In addition, the porous metal-organic framework including zinc on a zinc substrate is manufactured through a wet chemistry process, so that the process is simple and economical compared to the prior art for large-scale zinc-ion batteries. It may have the advantage of being able to provide an anode electrode.

In an embodiment according to an aspect of the present invention, the method of manufacturing an anode electrode for a zinc-ion battery may include preparing a zinc oxide-zinc (ZnO/Zn) composite by oxidizing one surface of a zinc substrate.

As described above, zinc oxide formed on one surface of the zinc substrate can have a higher reactivity compared to the natural oxide film of pure zinc in the process of forming the metal-organic framework, so that it can be used in the production of a porous metal-organic framework to be performed later. There is an advantage to it.

Specifically, in zinc oxide formed on one surface of the zinc substrate, oxygen anions bound to zinc cations are replaced with precursor anions dehydrogenated in aqueous precursor solution, so that zinc cations are combined with precursor dehydrogenated in aqueous precursor solution. converted into a metal-organic framework. That is, since the oxygen anion contained in the natural oxide film of pure zinc is limited, the conversion to the metal-organic framework may be remarkably slow or absent.

In an embodiment of the present invention, the thickness of the zinc substrate on which one surface is oxidized may be 10 to 1000 μm, specifically 100 to 500 μm, and more specifically 200 to 300 μm.

In an embodiment of the present invention, in the zinc oxide-zinc (ZnO/Zn) composite, the thickness of zinc oxide may be 0.1 to 200 μm, preferably 1 to 100 μm, and more preferably 10 to 60 μm. may be, and more preferably 20 to 40 μm. It is advantageous for the production of a porous metal-organic framework to be performed later, and zinc dendrites occurring in the zinc electrode due to the anode electrode for a zinc-ion battery having a structure of a porous metal-organic framework including zinc formed on a zinc substrate In order to solve the problem of short circuit caused by the growth of zinc oxide and to prevent side effects such as zinc corrosion, the thickness of the zinc oxide in the zinc oxide-zinc (ZnO/Zn) composite is preferably within the above range.

As an example of the present invention, oxidation of one surface of a zinc substrate is a physical vapor deposition (Physical Vapor Deposition) process such as sputtering, molecular beam epitaxy growth method, or various chemical vapor deposition processes It can be carried out through a laser deposition method, spray pyrolysis method, anodization method, electrostatic spray method, sol-gel process, wet precipitation method, etc., but by oxidizing one surface of the zinc substrate /Zn) complex can be produced, so it is satisfactory, so it is not limited thereto.

For the ease of the manufacturing process and the provision of a large-scale anode electrode for a zinc-ion battery, a zinc oxide-zinc (ZnO/Zn) composite is prepared by oxidizing one surface of a zinc substrate using a wet precipitation method. may be desirable.

For example, by immersing the zinc substrate in an aqueous solution containing one type of ammonium salt selected from ammonium persulfate, ammonium nitrate, ammonium chloride, tetramethylammonium chloride, tetramethylammonium nitrate and tetramethylammonium sulfate, A zinc oxide-zinc (ZnO/Zn) composite can be prepared by oxidizing the surface.

At this time, the concentration of the ammonium salt contained in the aqueous solution may be 0.1 to 10M, specifically 0.2 to 5M, may be more specifically 0.5 to 2M. The zinc substrate may be immersed in an aqueous solution containing an ammonium salt for 1 to 60 minutes, specifically for 1 to 30 minutes, and more specifically for 5 to 15 minutes. The temperature at which the zinc substrate is immersed in the aqueous solution containing the ammonium salt may be 10 to 50 °C, and specifically 20 to 30 °C.

The zinc substrate immersed in an aqueous solution containing an ammonium salt may be washed with deionized water after the immersion process.

When a zinc oxide-zinc (ZnO/Zn) composite is prepared using the wet precipitation method, the above conditions are satisfied for the production of a zinc oxide-zinc (ZnO/Zn) composite including zinc oxide having the above-described thickness. It is preferable that the immersion process is performed in the range.

In the method for manufacturing an anode electrode for a zinc-ion battery according to an aspect of the present invention, the zinc oxide-zinc (ZnO/Zn) complex is immersed in an aqueous precursor solution and dried, and then the porous metal-organic framework containing zinc on a zinc substrate. It may include manufacturing a (Zn-metal-organic framework, Zn-MOF).

In an embodiment, the aqueous precursor solution into which the zinc oxide-zinc (ZnO/Zn) complex is immersed may include an imidazole-based precursor.

In one embodiment, the concentration of the precursor included in the aqueous precursor solution may be 0.01 to 5M, specifically 0.05 to 2M, and more specifically 0.1 to 1M.

The imidazole precursor is benzimidazole, 2-methylbenzimidazole, 2-nitroimidazole, 5-nitrobenzimidazole, 5-chloro It may be at least one selected from benzimidazole (5-chlorobenzimidazole), 2-methylimidazole (2-methylimidazole), and 4-methylimidazole (4-methylimidazole).

In an embodiment, the aqueous precursor solution may include a solution in which an imidazole-based precursor is dissolved in a polar solvent.

Polar solvents are methanol, ethanol, methoxyethanol, ethoxyethanol, propanol, isopropanol, tert-butanol, n-butanol, isobutanol, dimethylacetamide, dimethylformamide, n-methyl-2-pyrrolidone (NMP ), formic acid, nitromethane, acetic acid and distilled water may be at least one selected from the group consisting of.

In one embodiment, the zinc oxide-zinc (ZnO/Zn) complex may be immersed in the precursor aqueous solution for 4 to 24 hours, specifically for 8 to 20 hours, and more specifically for 10 to 18 hours. can be immersed. For the preparation of a porous metal-organic framework containing zinc on a zinc substrate from a zinc oxide-zinc (ZnO/Zn) composite, the zinc oxide-zinc (ZnO/Zn) composite is immersed in an aqueous precursor solution for a time in the above range. it is preferable

The temperature at which the zinc oxide-zinc (ZnO/Zn) composite is immersed in the aqueous precursor solution may be room temperature, specifically 15 to 30°C, and more specifically 20 to 28°C.

In an embodiment of the present invention, the method may include immersing the zinc oxide-zinc (ZnO/Zn) composite in an aqueous precursor solution, washing and drying in an oven.

Drying in the oven may be carried out in a temperature range of 30 to 200 °C, specifically in a temperature range of 50 to 150 °C, and more specifically in a temperature range of 60 to 100 °C. The drying time may be 0.5 to 10 hours, may be 1 to 5 hours, may be 2 to 4 hours, but is not limited thereto because it is satisfactory when the residual polar solvent is removed.

While the zinc oxide-zinc oxide (ZnO/Zn) complex is immersed in the aqueous precursor solution, the zinc oxide layer can be etched by the aqueous precursor solution, and the oxygen anions contained in the zinc oxide layer are deprotonated in the aqueous precursor solution with the precursor anions. By replacement, the zinc cation can be converted into a metal-organic framework bound to the deprotonated precursor in the aqueous precursor solution.

According to an embodiment of the present invention, the metal-organic framework may be derived from zinc oxide.

In this case, the metal-organic framework may be a monolithic layer formed by directly growing on the surface of a zinc oxide-zinc (ZnO/Zn) composite.

As described above, while the zinc oxide-zinc (ZnO/Zn) complex is immersed in the aqueous precursor solution, the zinc oxide layer is etched by the aqueous precursor solution, and zinc cations present on the surface of the zinc layer are dehydrogenated in the aqueous precursor solution (deprotonation). ) and converted into a metal-organic framework, the metal-organic framework can be grown directly on the surface of the zinc oxide-zinc oxide (ZnO/Zn) composite on which the zinc oxide layer is etched.

The anode electrode for zinc-ion batteries is a short circuit that can be caused by the growth of zinc dendrites by directly growing on the surface of the etched zinc oxide-zinc (ZnO/Zn) composite and densely bonding the metal-organic framework with the surface. It can solve the problem of and can have the advantage of preventing side effects such as zinc corrosion.

In addition, the metal-organic framework may be a monolithic layer conformally formed on the surface of the etched zinc oxide-zinc (ZnO/Zn) composite.

In an embodiment of the present invention, the metal-organic framework may be a zeolitic imidazolate framework (ZIF).

In one embodiment, the metal-organic framework may be a zeolite-type imidazolate structure that is a crystalline porous material prepared by arranging zinc metal ions and an imidazolate ligand. Specifically, the zeolite-type imidazolate structure may be ZIF-8.

In one embodiment, the porous metal-organic framework may include micropores.

A pore is defined as microporous if its size is 2 nm or less according to the definition of IUPAC, is defined as mesoporous if its size is 2 to 50 nm, and macroporous if its size is 50 nm or more. Defined.

That is, the size of the pores included in the porous metal-organic framework may be 0.01 to 4 nm, specifically 0.05 to 2 nm, and more specifically 0.1 to 2 nm.

As described above, in the method for manufacturing an anode electrode for a zinc-ion battery according to an embodiment of the present invention, zinc oxide is formed on one surface of a zinc substrate by oxidizing one surface of a zinc substrate-zinc-zinc (ZnO/Zn) After preparing the composite, the anode electrode for a zinc-ion battery in which a porous metal-organic framework containing zinc is prepared on a zinc substrate through a wet chemistry process in which the composite is immersed in a precursor aqueous solution and dried Since it provides a method to be used, it has the advantage of being able to provide a zinc-ion battery anode electrode of not only small-scale, but also large-scale, in a simple and economical way compared to the prior art. That is, the zinc, which may be provided - but not the ion cell area of the anode limited, For example, zinc-ion battery, the area of the anode electrode is 0.001 to 10000cm can ^2, 0.001 to 5000cm can ^2, 0.001 to 2000cm ^It can be two.

In an embodiment according to an aspect of the present invention, in a method for manufacturing an anode electrode for a zinc-ion battery, a zinc oxide-zinc (ZnO/Zn) complex is immersed in an aqueous precursor solution and dried, and then a porous metal containing zinc on a zinc substrate. - It may further include the step of pyrolysis after the step of manufacturing the organic framework (Zn-metal-organic framework, Zn-MOF).

Pyrolysis refers to the conversion of a material into one or more other materials. In one embodiment, the organic material included in the porous metal-organic framework may be converted into a solid residue rich in carbon content through the pyrolysis step.

For example, the organic material included in the porous metal-organic framework can be converted into nitrogen-doped carbon having excellent conductivity, which solves the problem of short circuit caused by zinc dendrites occurring in the zinc electrode, and side effects such as zinc corrosion It can be prevented and can have the advantage of providing an anode electrode for a zinc-ion battery excellent in cycle life, high-efficiency plating-stripping performance, and safety.

Thermal decomposition may occur in an inert atmosphere that is an Ar or N ₂ gas atmosphere, and may occur in an atmosphere containing _{reactive gases such as NH 3} , O ₂ , air, CO ₂ or H _{2 .}

In an embodiment, the thermal decomposition _{may be carried out in a gas atmosphere in which H 2} and Ar are mixed, and in the total volume of the gas, H ₂ may contain 0.1 to 10% by volume, specifically 0.5 to 10% by volume. It may be, and more specifically, 1 to 10% by volume may be included.

In one embodiment of the present invention, the thermal decomposition may be carried out in a temperature range of 400 to 900 ℃, specifically, it may be carried out in a temperature range of 600 to 900 ℃.

Since the boiling point of zinc metal is 907° C., in order to prevent loss of zinc due to vaporization during the thermal decomposition process of the porous metal-organic framework including zinc, the thermal decomposition is preferably performed in the above temperature range.

In one embodiment, the heating rate during thermal decomposition may be 20 to 100 °C/s, preferably 40 to 100 °C/s, and more preferably 50 to 90 °C/s.

In one embodiment, the pyrolysis may be performed for 1 to 30 minutes, specifically for 1 to 20 minutes, more specifically for 1 to 10 minutes, and even more specifically for 2 to 8 minutes. can be performed for minutes.

Even if thermal decomposition is performed in the above temperature range, if the heating rate during thermal decomposition is slow, zinc loss due to vaporization of zinc metal may occur.

The anode electrode for a zinc-ion battery according to another aspect of the present invention includes a zinc metal substrate; and a porous metal-organic framework layer disposed on a zinc metal substrate and characterized in that the surface of the porous metal-organic framework layer containing zinc is hydrophilic.

In detail, hydrophilicity may be expressed as a water contact angle, which is a measure of surface wettability. The hydrophilic surface of the porous metal-organic framework layer including zinc may mean that the water contact angle of the porous metal-organic framework layer including zinc is low compared to the water contact angle of the zinc metal substrate.

For example, the water contact angle of the porous metal-organic framework layer including zinc may be 65 to 90°, specifically 70 to 90°, and more specifically 75 to 85°.

In an embodiment of the present invention, the hydrophilic metal-organic framework layer may satisfy Equation 1 below.

(Equation 1)

θ ₁ = xθ ₂ (1.1 ≤ x ≤ 1.4)

In this case, θ ₁ in Equation 1 is the water contact angle of the zinc metal substrate, and θ ₂ is the water contact angle of the metal-organic framework layer.

Specifically, x may satisfy 1.1 to 1.4, 1.1 to 1.3, or 1.1 to 1.2.

Because the porous metal-organic framework layer containing zinc has hydrophilic characteristics, it means that ions on the electrolyte can easily access the anode electrode for zinc-ion batteries, which results in high-efficiency plating-stripping (plating-stripping). stripping) may have the effect of providing an anode electrode for a zinc-ion battery having performance.

In an embodiment of the present invention, the thickness of the zinc metal substrate may be 10 to 1000 μm, specifically 100 to 500 μm, more specifically 200 to 300 μm.

In one embodiment, the thickness of the porous metal-organic framework layer comprising zinc may be 0.1 to 100 μm, preferably 1 to 80 μm, more preferably 10 to 60 μm, More preferably, it may be 20 to 40 μm.

As described above, the porous metal-organic framework layer including zinc positioned on the zinc metal substrate is densely bonded to the surface of the zinc metal substrate to form a monolithic conformal on the surface of the zinc metal substrate. It may be a monolithic layer.

In one embodiment of the present invention, the metal-organic framework may be a zeolitic imidazolate framework (ZIF).

In one embodiment of the present invention, the metal-organic framework may be a zeolite-type imidazolate structure that is a crystalline porous material prepared by arranging zinc metal ions and an imidazolate ligand. Specifically, the zeolite-type imidazolate structure may be ZIF-8.

In one embodiment, the porous metal-organic framework may include micropores.

Micropores are defined as pores having a size of 2 nm or less by the definition of IUPAC.

For example, the size of the pores included in the porous metal-organic framework may be 0.01 to 2 nm, specifically 0.05 to 2 nm, and more specifically 0.1 to 2 nm.

As such, since the anode electrode for a zinc-ion battery includes the porous metal-organic framework, ions included in the electrolyte may diffuse through the porous metal-organic framework layer. Due to this, it is possible to minimize the formation of zinc dendrites in the anode electrode for a zinc-ion battery, and to enable uniform charge distribution during a plating-stripping cycle.

According to another aspect of the present invention, an anode electrode for a zinc-ion battery includes a zinc metal substrate; and a porous carbon layer disposed on the zinc metal substrate and doped with nitrogen.

Specifically, the porous carbon layer doped with nitrogen may be prepared by thermally decomposing a metal-organic framework. It may be prepared by thermal decomposition of an organic material included in the metal-organic framework to be converted into a porous carbon layer doped with nitrogen.

For example, the porous carbon layer doped with nitrogen may contain 1 to 40 atomic % nitrogen, specifically 5 to 30 atomic % nitrogen, and more specifically 5 to 25 atomic % nitrogen may contain, and more specifically, may contain 10 to 20 atomic% of nitrogen.

In one embodiment, the doped nitrogen is a nitrogen type having a pyridinic-N configuration, a nitrogen type having a pyrrolic-N configuration, a nitrogen type having a graphitic-N configuration and at least one nitrogen type selected from nitric oxide.

In one embodiment of the present invention, the doped nitrogen may contain 20 to 90 atomic %, specifically 30 to 90 atomic %, of a nitrogen type having a pyridine-like (pyridinic-N) arrangement, more Specifically, it may include 40 to 90 atomic%.

At this time, the nitrogen site doped in the porous carbon layer may accommodate zinc cations and may have the effect of facilitating movement to the electrode surface. In addition, it has the advantage of effectively suppressing the formation of zinc dendrites by enabling uniform charge distribution.

In an embodiment of the present invention, the thickness of the zinc metal substrate may be 10 to 1000 μm, specifically 100 to 500 μm, more specifically 200 to 300 μm.

In one embodiment, the thickness of the porous carbon layer doped with nitrogen may be 0.1 to 100 μm, preferably 1 to 80 μm, more preferably 10 to 60 μm, even more preferably For example, it may be 20 to 40 μm.

In one embodiment of the present invention, the porous carbon layer may be porous disordered graphitic carbon.

In one embodiment, the porous carbon layer may include macropores.

The macropore may mean pores having a size of 50 nm or more by the definition of IUPAC, and for example, the size of the pores included in the porous carbon layer may be 60 nm to 5 μm, and specifically 100 nm to 3 μm. , more specifically 500 nm to 2 μm.

In one embodiment of the present invention, the surface of the porous carbon layer doped with nitrogen may be hydrophilic.

In detail, hydrophilicity may be expressed as a water contact angle, which is a measure of surface wettability. The fact that the surface of the porous carbon layer doped with nitrogen is hydrophilic may mean that the water contact angle of the porous carbon layer doped with nitrogen is lower than the water contact angle of the zinc metal substrate.

For example, the water contact angle of the porous carbon layer doped with nitrogen may be 10 to 90°, specifically 15 to 70°, and more specifically 20 to 50°.

In an embodiment of the present invention, the hydrophilic metal-organic framework layer may satisfy Equation 2 below.

(Equation 2)

θ ₁ = xθ ₂ (1.5 ≤ x ≤ 4.0)

In this case, θ ₁ in Equation 2 is the water contact angle of the zinc metal substrate, and θ ₂ is the water contact angle of the porous carbon layer doped with nitrogen.

Specifically, x may satisfy 1.5 to 4.0, 1.7 to 4.0, or 2.0 to 4.0.

Since the porous carbon layer doped with nitrogen has hydrophilic characteristics, it means that ions on the electrolyte can easily access the anode electrode for zinc-ion batteries, which results in high-efficiency plating-stripping performance. It may have the effect of providing an anode electrode for a zinc-ion battery having a.

As described above, the anode electrode for a zinc-ion battery according to another aspect of the present invention includes a zinc metal substrate; and a porous carbon layer disposed on a zinc metal substrate and doped with nitrogen; by including, the anode electrode for a zinc-ion battery is a zinc dendrite due to the nitrogen content, porosity and hydrophilicity contained in the anode electrode for a zinc-ion battery It can provide the advantage of improving the cycle life of zinc-ion batteries based on the excellent reversibility of zinc plating-stripping performance by effectively inhibiting the formation of zinc-ion batteries.

Hereinafter, the present invention will be described in more detail through Examples and Experimental Examples.

(Example 1)

After attaching Kapton tape to one side of a Zn foil with a diameter of 8mm and a thickness of 250μm, it is immersed in 1M ammonium persulfate (APS) aqueous solution for 10 minutes and then washed with deionized water to oxidize. A zinc-zinc (ZnO/Zn) composite was prepared. Then, the zinc oxide-zinc (ZnO/Zn) complex was immersed in an aqueous solution containing 0.5 M 2-methylimidazole (HMI) for 14 hours and washed with deionized water. Thereafter, it was dried in an oven at 80° C. for 3 hours to prepare a porous metal-organic framework containing zinc positioned on a zinc foil, which was named ZIF-8/Zn.

(Example 2)

ZIF-8/Zn of Example 1 was pyrolyzed at a temperature of 650° C. under a gas atmosphere _{in which H 2} and Ar were mixed in a furnace built in a laboratory that reached the target temperature in 10 seconds. At this time, 5% by volume of H ₂ was included in the mixed gas atmosphere. ZIF-8/Zn was prepared by pyrolysis for 5 minutes, which was named C-650/Zn.

(Example 3)

It was prepared in the same manner as in Example 2, but was prepared by thermal decomposition at a temperature of 750° C., which was named C-750/Zn.

(Example 4)

It was prepared in the same manner as in Example 2, but was prepared by thermal decomposition at a temperature of 840° C., which was named C-840/Zn.

(Comparative Example 1)

One side of the zinc foil having a diameter of 8 mm and a thickness of 250 μm used in Example 1 was zinc attached with a Kapton tape, and this was named Zn.

(Comparative Example 2)

It was prepared in the same manner as in Example 1, except that only a zinc oxide-zinc (ZnO/Zn) composite was prepared, which was named ZnO/Zn.

In one embodiment, the present invention Comparative Example 1, Comparative Example 2 and having an electrode area larger the anode electrode of the size can be economically produced using wet chemical processes, is also 1a, 1b and 1c, respectively 1350cm ² It is a figure which shows the actual optical photograph of Example 1.

(Experimental Example 1) Analysis of shape, structure, and surface chemical state of the prepared anode electrode for zinc-ion batteries

The shape, structure, and chemical state of the surface of the prepared anode electrode for a zinc-ion battery were analyzed by scanning electron microscopy (SEM, Verios 460, FEI), X-ray diffraction in the range of 10 to 80° 2θ (XRD, Rigaku Smartlab, 40 kV, 200 mA, Cu-Kα radiation, λ = 0.15418 nm), Raman spectroscopy (WITec GmbH Raman microscope, 1 mW power, 532 nm laser) and X-ray photoelectron spectroscopy (XPS, ThermoFisher, K-alpha).

Figure 2a shows a schematic diagram in which Comparative Example 2, Examples 1, and Examples 2 to 4 are sequentially prepared from Comparative Example 1.

2b1, 2b2, 2b3, 2b4, 2b5 and 2b6 show SEM images of Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3 and Example 4, respectively; 2C is a diagram showing an optical photograph of each sample.

As shown in FIG. 2B , it was confirmed that each electrode exhibited a continuous and uniform surface characteristic, and in particular, Examples 2 to 4 showed a porous surface including macropores.

2d1, 2d2, and 2d3 are cross-sectional SEM images and energy dispersive X-ray spectroscopy (EDS) element mapping images of Comparative Example 2, Example 1 and Example 3, respectively. Comparative Example 2 (ZnO/ Zn) confirmed that Zn and O elements were uniformly distributed, and in Example 1 (ZIF-8/ZnO), it was confirmed that the distribution of O elements was lower than that of Zn, C and N elements, which It can be seen that the formation of the layer results from the chemical etching of the ZnO layer. Additionally, in the case of Example 3 (C-750/Zn), it was confirmed that the elements of Zn, C, O and N were uniformly distributed.

Chemical compositions of Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3, and Example 4 measured from EDS are summarized in Table 1 below.

Each prepared anode electrode was analyzed by performing XRD analysis. 3A is a view showing the measured XRD patterns of Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3 and Example 4, and FIG. 3B is a view simulating the XRD pattern of ZIF-8. am.

Characteristic peaks of Zn corresponding to (002), (100) and (101) planes were observed at 36.4°, 39.2°, and 43.8°, respectively, for each of the prepared anode electrodes, and in the case of Example 1, 5 to 30° A specific peak was observed in the range of , which was confirmed to be consistent with the simulated peak of ZIF-8.

In addition, it can be seen from the weak peak at 7.5° observed in Example 2 that some carbonization of ZIF-8 progressed, and in Examples 3 to 4, a peak similar to that of ZIF-8 was not observed, so ZIF- 8 was completely decomposed, and it was confirmed that a carbon structure doped with nitrogen was formed.

The structure of each prepared anode electrode was further analyzed by performing Raman spectroscopy.

4 is a view showing Raman spectra of Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3, and Example 4;

As shown in Fig. 4, ^{the Raman band at 563 cm −1} observed in Example 1 is due to the A ₁ (LO) phonon mode in ZnO related to oxygen vacancy, 686, 1145 and 1459 cm. ^{The Raman bands at −1 result} from deformation of the imidazole ring, CN stretching and bending of the CH plane, respectively. Additionally, it was confirmed that the Raman band resulting from the C=C stretching ^{was observed at 1505 cm −1 .} The Raman bands observed at 2928 and 3134 cm ⁻¹ are due to CH stretching and are due to bonding of methyl and imidazole functional groups, respectively.

In Examples 2 to 4, Raman bands related to ZnO and ZIF-8 were not observed, and it was confirmed that D and G bands were present at ^{1328 and 1582 cm -1 , respectively.} From this, it can be seen that porous and disordered graphitic carbon was formed.

The chemical state of the surface of each prepared anode electrode was performed through XPS analysis.

5 is a diagram illustrating XPS survey spectra of an anode electrode, respectively. As shown in FIG. 5 , it was confirmed that Zn, O, N and C elements were present in the same manner as the previous ESD results.

6 is a diagram showing high-resolution spectra of the C1s peak observed in Examples 1 to 4;

In the case of Example 1, it was confirmed that CC and CN bonds were present from the peaks observed at 284.5 and 285.7 eV, respectively, and the presence of CO and C = O bonds was confirmed from the peaks observed at 287.7 eV in Examples 2 to 4. . The presence of such a bond with oxygen is derived from oxygen remaining during the decomposition of ZIF-8, oxygen contained in ZiF-8 incompletely converted from ZnO, and oxygen contained in the air during the handling process of the samples of Examples 2 to 4 may be due to

The binding energy and composition at which the peaks of the deconvolved spectra of the C1s peaks observed in Examples 1 to 4 are located are shown in Table 2 below.

7 is a diagram showing high-resolution spectra of the N1s peak observed in Examples 1 to 4;

As shown in FIG. 7 , it was confirmed that nitrogen has a nitrogen type having a pyridinic-N arrangement and a nitrogen type having a graphitic-N arrangement, and the deconvolved spectrum of the N1s peak is The binding energy and composition at which the peak is located are shown in Table 3 below.

(Experimental Example 2) Confirmation of wettability of the prepared zinc anode electrode

During the zinc plating-stripping cycle, the wettability of the surface of each prepared electrode required for the formation of a uniform zinc plating film was evaluated. Wettability was evaluated by measuring the water contact angle, and the water contact angle was measured using the SEO Phoenix-I system.

8 is a view showing the water contact angle of Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3, and Example 4.

As shown in FIG. 8 , it was confirmed that Examples 1 to 4 had a lower water contact angle compared to Comparative Examples 1 and 2, and it was confirmed that the electrode surfaces of Examples 1 to 4 were modified to have hydrophilic properties.

As the electrode surfaces of Examples 1 to 4 have hydrophilic properties, it means that ions on the electrolyte can easily access the anode electrode for a zinc-ion battery, which is a high-efficiency plating-stripping performance In addition to having a , it is possible to form a uniform plating film, it is possible to effectively suppress the formation of zinc dendrites.

(Experimental Example 3) Confirmation of electrochemical properties of the prepared zinc anode electrode

The plating-stripping performance test of the anode electrode was performed by two-electrode and three-electrode experiments.

First, in the two-electrode experiment, a stainless steel current collector was applied as a counter electrode, and the experiment was _{performed in 1M ZnSO 4} aqueous electrolyte solution.

9A is a diagram illustrating a profile of a cyclic voltammetry (CV) curve performed at a scan rate of 0.2 mV/s in a two-electrode experiment. As shown in Fig. 9a, it was confirmed that all anode electrodes had a similar CV profile, and it was confirmed that they provided a high current density, from which Comparative Examples 1, 2, Example 1, Example 2, and Example 3 And it can be seen that the electrode of Example 4 has excellent performance as a material of the anode electrode.

In addition, the CV profile of the anode electrode was measured in a three-electrode system comprising a Zn foil as a reference electrode and a graphite foil as a counter electrode. The experiment was repeated for 300 cycles at a scanning rate of 20 mV/s within the range of 0 to 2V in _{1M of ZnSO 4 aqueous electrolyte.} As a result, it was confirmed that all anode electrodes showed the same (identical) CV profile (FIG. 9b).

Additionally, in preparing Example 4 for simultaneous comparison of the anode electrodes of Comparative Examples 1 and 4, a modified anode electrode was prepared after attaching a Kapton tape to the central part of the zinc foil did. Fig. 9c is a schematic diagram of a modified anode electrode, and Fig. 9d shows an SEM image of the modified anode electrode.

That is, the anode electrode in which Comparative Example 1 (Zn) and Example 4 (C-840 / Zn) co-existance was analyzed in the same way as the three-electrode system performed above, after repeated experiments for 300 cycles. (Fig. 9e).

As shown in FIG. 9E , formation of sharp zinc flakes of relatively large size was observed in the central portion of the modified electrode, that is, the Zn region, while the outer portion of the modified electrode, that is, C-840/Zn In the region, the growth of dendrite-type zinc flakes was not observed, and from this, it can be seen that Example 4 (C-840/Zn) had an excellent effect in inhibiting the growth of zinc dendrites and protecting from zinc corrosion. have.

(Experimental Example 4) Confirmation of long-term electrochemical performance and stability of the prepared zinc anode electrode

Long-term electrochemical performance and stability of the anode electrode were investigated using a symmetrical cell in 2M ZnSO _{4 electrolyte.} 10A and 10B are diagrams showing the cycle stability of each anode electrode in a current density ranging from 1 to 10 mA/cm ^{2 and a capacity ranging from 1 to 10 mAh/cm 2 .}

During 200 cycles of zinc plating-stripping, small voltage fluctuations were observed in the Zn cells (Zn | Zn) at a ^{current density of 1 mA/cm 2 and a capacity of 1} mAh/cm 2 , Comparative Example 2 and It was confirmed that each of the symmetric cells of Examples 1 to 4 had high stability. When the current density ^{was increased to 2mA/cm 2} , a short circuit occurred in the Zn cell, and it was confirmed that the battery failed after 150 cycles. On the other hand, each symmetrical cell composed of different anode electrodes still showed high stability.

At a high current density of 5mA/cm ² , the Zn cell failed after 75 cycles, and the ZnO/Zn cell failed after 162 cycles. It was confirmed that stability was shown.

When the current density ^{was increased to 10mA/cm 2} , the Zn cell showed thermal electrochemical performance, a short circuit was confirmed after 72 cycles, and the ZnO/Zn cell failed after 162 cycles. On the other hand, Examples 1 and 2 showed a small increase in polarization, but showed high stability, and it was confirmed that Examples 3 to 4 still had high stability. As such, it can be seen that each of the symmetric cells of Examples 1 to 4 has higher stability than the symmetric cells of Comparative Example 1 or Comparative Example 2.

Additionally, the morphology of each anode electrode surface after a cycle of plating-stripping was observed.

11A, 11B, 11C, 11D, 11E, and 11F show the zinc of each symmetric cell composed of Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3 and Example 4, respectively. It is a diagram showing an SEM image of each anode electrode measured after a plating-stripping cycle.

As shown in Fig. 11a, after the cycle, Comparative Example 1 had a morphology having a surface with large-sized sharp zinc flakes, and the surface of Comparative Example 2 was also observed to form zinc flakes (Fig. 11b), which was, It can be seen that a short circuit is induced in the symmetric cell and eventually the symmetric cell fails, which is not stable.

In contrast, it was confirmed that the electrode surface of Example 1 after the cycle had a flat and uniform surface without zinc flakes. In addition, as a result of observation of the surfaces of Examples 2 to 3 after the cycle, it was confirmed that the porous carbon layer was maintained, and the formation of zinc dendrites was also not found. Due to the characteristic of porosity of the anode electrodes of Examples 1 to 4, during the zinc plating-stripping process, the distribution of zinc cations contained in the electrolyte solution in the anode electrode is uniformly distributed to prevent the formation of zinc dendrites. that can be effectively suppressed.

(Experimental Example 5) Performance evaluation of an aqueous zinc-ion battery (ZIB) including a prepared zinc anode electrode

To evaluate the stability and lifespan of the anode electrode, MnO ₂ nanowire was applied as a cathode electrode material, and the efficiency was evaluated in an aqueous zinc-ion battery (ZIB) including each prepared anode electrode.

At this time, the MnO _{2 nanowire was dissolved in 10 mM KMnO 4} and 10 mM NH 4 Cl in 70 mL of deionized water, and then the solution was put into a 100 mL Teflon-lined hydrothermal reactor and 150° C. for 16 hours. was maintained at a temperature of The resultant, naturally cooled to room temperature, was washed with deionized water and dried in an oven at 80° C. for 6 hours.

After that, the cathode electrode was _{prepared by mixing the MnO 2} nanowires obtained above, carbon black (Super P) and a PTFE binder in a weight ratio of 8:1:1, and then using ethanol to prepare a mixed slurry, and then a disk shape with a diameter of 8mm After preparation, it was prepared by drying in a vacuum oven at 80° C. for 12 hours.

Finally, the cathode electrode prepared above, _{an aqueous electrolyte containing 2M of ZnSO 4} and 0.1M of MnSO ₄ , and each of Comparative Examples 1, 2, 1, 2, 3 and 4 was constituted as an anode electrode to prepare each aqueous ZIB.

12A is a diagram showing the CV profile of each water-based ZIB prepared. CV was performed at a scan rate of 0.1 mV/s in the range of 1.0 to 2.0 V.

As shown in Fig. 12a, similar CV profiles were observed for each water-based ZIB, and it can be seen that the confirmed high current responsiveness is due to the rapid kinetics of zinc deposition and decomposition during CV performance. In addition, the two reduction peaks identified at 1.25 and 1.38V originate from zinc ions inserted into the _{MnO 2} cathode electrode, and are the result of reduction of ^{Mn 4+} to the Mn ³⁺ state, followed by reduction to the Mn ^{2+ state.}

12B, 12C and 12D are diagrams showing the cycle performance of each water-based ZIB at each current rate (C-rate) 0.1, 0.5, and 1C. Here, the C-rate is a unit for predicting or indicating the current value setting and the possible use time of the battery under various usage conditions during charging and discharging of the battery.

In Examples 1 to 4, it was confirmed that each of the aqueous ZIBs including the anode electrode exhibited excellent cycle performance and high Coulombic efficiency (CE).

Water-based ZIB including Comparative Example 1 as an anode electrode failed after 700 cycles at a C-rate of 1.0, which can be seen from the formed zinc dendrite. In addition, the growth of zinc dendrites was also observed in the aqueous ZIB including Comparative Example 2 as an anode electrode.

From this, it was confirmed that Examples 1 to 4 each water-based ZIB including the anode electrode has excellent long-term lifespan at various C-rates, which means that the anode electrode of Examples 1 to 4 is the fail of the water-based ZIB battery. This is because it can effectively inhibit the growth of zinc dendrites that cause zinc dendrites and effectively prevent side effects such as zinc corrosion.

As described above, the present invention has been described with specific matters and limited examples and drawings, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention is not limited to the above embodiments. Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (20)

a) preparing a zinc oxide-zinc (ZnO/Zn) composite by oxidizing one surface of a zinc substrate; and
b) The zinc oxide-zinc (ZnO/Zn) composite was immersed in a precursor aqueous solution and dried to prepare a porous metal-organic framework (Zn-MOF) containing zinc on a zinc substrate A method of manufacturing an anode electrode for a zinc-ion battery comprising; The method of claim 1,
The metal-organic framework is a zinc oxide-zinc (ZnO/Zn) composite, which is a monolithic layer formed by growing directly on the surface of a zinc-ion battery. 3. The method of claim 2,
The metal-organic framework is a zeolitic imidazolate framework (ZIF), a method of manufacturing an anode electrode for a zinc-ion battery. 4. The method of claim 3,
The zeolite-type imidazolate structure is ZIF-8, a method of manufacturing an anode electrode for a zinc-ion battery. The method of claim 1,
The precursor aqueous solution is a zinc-ion method for producing an anode electrode for a battery containing an imidazole-based precursor. The method of claim 1,
The porous metal-organic framework is a method of manufacturing an anode electrode for a zinc-ion battery comprising micropores. The method of claim 1,
After step b), the method of manufacturing an anode electrode for a zinc-ion battery further comprising the step of thermally decomposing. 8. The method of claim 7,
A method of manufacturing an anode electrode for a zinc-ion battery wherein the heating rate during the thermal decomposition is 50 to 90 °C/s. 9. The method of claim 8,
The thermal decomposition is carried out in a temperature range of 500 to 900 ℃ zinc-ion method of manufacturing an anode electrode for a battery. 10. The method of claim 9,
The pyrolysis is performed for 1 to 10 minutes. A method of manufacturing an anode electrode for a zinc-ion battery. zinc metal substrate; and
A porous metal-organic framework layer located on the zinc metal substrate and containing zinc; including,
The anode electrode for a zinc-ion battery, characterized in that the surface of the porous metal-organic framework layer is hydrophilic. 12. The method of claim 11,
The hydrophilic metal-organic framework layer is a zinc-ion battery anode electrode satisfying Equation 1 below.
(Equation 1)
θ ₁ = xθ ₂ (1.1 ≤ x ≤ 1.4)
(θ ₁ in Equation 1 is the water contact angle of the zinc metal substrate, and θ ₂ is the water contact angle of the metal-organic framework layer) 12. The method of claim 11,
The metal-organic framework is a zeolitic imidazolate framework (ZIF) anode electrode for a zinc-ion battery. 14. The method of claim 13,
The zeolite-type imidazolate structure is ZIF-8 zinc-ion battery anode electrode. zinc metal substrate; and
A zinc-ion battery anode electrode comprising a; located on the zinc metal substrate, a porous carbon layer doped with nitrogen. 16. The method of claim 15,
The nitrogen-doped porous carbon layer is a zinc-ion battery anode electrode prepared by thermal decomposition of the metal-organic framework. 17. The method of claim 16,
The porous carbon layer doped with nitrogen contains 5 to 25 atomic% of nitrogen as an anode electrode for a zinc-ion battery. 16. The method of claim 15,
The nitrogen-doped porous carbon layer satisfies Equation 2 below: an anode electrode for a zinc-ion battery.
(Equation 2)
θ ₁ = xθ ₂ (1.5 ≤ x ≤ 4.0)
(θ ₁ in Equation 2 is the water contact angle of the zinc metal substrate, and θ ₂ is the water contact angle of the porous carbon layer doped with nitrogen) 16. The method of claim 15,
The porous carbon layer is a zinc-ion battery anode electrode comprising macro pores. A rechargeable water-based zinc-ion battery comprising the anode electrode for a zinc-ion battery according to any one of claims 11 to 19.

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