Artificial solid electrolyte interphase film regulated zinc ion battery anode and applications

Abstract

The application belongs to the field of zinc ion batteries, and discloses a zinc ion battery negative electrode regulated by an artificial solid electrolyte interface film and application. The zinc ion battery negative electrode regulated by the artificial solid electrolyte interface film is obtained by placing a metal zinc negative electrode in a first atmosphere and a second atmosphere for first plasma treatment and second plasma treatment, respectively, so that the zinc ion battery negative electrode has a surface with an artificial solid electrolyte interface film. The first atmosphere is a carbon-containing atmosphere, and the second atmosphere is a carbon-free atmosphere. Through twice plasma treatment under specific atmospheres, the metal zinc negative electrode with an originally low-quality initial artificial solid electrolyte interface film obtained by one-time treatment is further treated, so that the wettability of the electrolyte can be effectively improved, the corrosion process of the metal zinc negative electrode can be reduced, the generation of dendrites can be relieved, and the cycle performance of the metal zinc negative electrode can be improved.

Description

Technical Field

[0001] This invention belongs to the field of zinc-ion batteries, and more specifically, relates to a zinc-ion battery anode and its application based on an artificial solid electrolyte interface membrane. The artificial solid electrolyte interface membrane of the zinc metal anode is regulated by a secondary plasma strategy (such as a secondary room temperature plasma strategy), and the cycle stability of the zinc metal anode is improved by interface modification. This invention efficiently realizes the interface modification and structural engineering of the artificial solid electrolyte interface membrane of the zinc metal anode. Background Technology

[0002] The development and application of energy storage systems provide necessary technical support for the full development of renewable energy and have stimulated the enthusiasm of researchers.

[0003] Multivalent metal ion rechargeable batteries, including those using Ca, Al, and Zn, have been widely developed due to their high energy density, low cost, and abundant resources. Among these, only zinc anodes exhibit high compatibility with aqueous electrolytes. Furthermore, aqueous electrolytes can endow batteries with inherent chemical safety and environmental friendliness. Therefore, rechargeable aqueous zinc-ion batteries (AZIBs) are considered promising candidates for large-scale energy storage systems. However, the interfacial problems of zinc anodes severely affect the stability and cycle life of AZIBs. Therefore, exploring modification strategies for zinc anodes to obtain AZIBs with high stability and long lifespan is a research hotspot.

[0004] Interface engineering is an effective strategy for regulating zinc ion deposition behavior, which can effectively alleviate zinc dendrite growth and side reactions at the zinc anode. Artificial solid electrolyte interface films on the surface can reduce direct contact between the zinc anode and water molecules in the electrolyte, suppress side reactions on the zinc anode surface, and improve cycle performance. To date, many methods have been developed as electrode candidate materials and applied to AZIBs, but common problems such as cumbersome and complex processing methods and poor cycle stability still exist.

[0005] Plasma treatment (especially room temperature plasma treatment) is characterized by its simplicity. Existing technologies also employ single-pass plasma treatment of zinc metal anodes. Taking CF4 plasma treatment as an example, the formation of a carbon film and trace amounts of ZnF2 can contribute to uniform ion deposition to some extent (the carbon film and trace amounts of ZnF2 ensure uniform deposition of Zn ions on the zinc sheet during subsequent battery applications, suppressing dendrite formation). However, due to the low ZnF2 content, the cycle performance of zinc metal anodes modified with a small amount of ZnF2 is still in its early stages. Problems such as dendrite formation, poor cycle performance, low quality, low discharge capacity, and high impedance when assembled with the positive electrode still require improvement. Summary of the Invention

[0006] To address the aforementioned deficiencies or improvement needs of existing technologies, the present invention aims to provide a zinc-ion battery anode and its application based on an artificial solid electrolyte interface film (AES). This is achieved by improving the processing technology. A zinc anode without an AES is first pretreated in a carbon-containing plasma atmosphere (i.e., first plasma treatment) to obtain a low-quality initial AES modified zinc anode. Then, it is post-treated in a carbon-free plasma atmosphere (i.e., second plasma treatment). Through these two plasma treatments under specific atmospheres, utilizing the high chemical activity of plasma, and through chemical bonding, the initial low-quality AES-modified zinc anode is further post-treated to improve electrolyte wettability, reduce corrosion, alleviate dendrite formation, and enhance cycle performance.

[0007] To achieve the above objectives, according to one aspect of the present invention, a zinc-ion battery anode controlled by an artificial solid electrolyte interface film is provided, characterized in that the zinc-ion battery anode controlled by the artificial solid electrolyte interface film is obtained by first placing a metallic zinc anode without an artificial solid electrolyte interface film in a plasma of a first atmosphere for a first plasma treatment, and then in a plasma of a second atmosphere for a second plasma treatment, thereby obtaining a zinc-ion battery anode with an artificial solid electrolyte interface film on its surface.

[0008] The first atmosphere is a carbon-containing atmosphere, and the second atmosphere is a carbon-free atmosphere.

[0009] As a further preferred embodiment of the present invention, the carbon-containing atmosphere is selected from C1-C8 alkanes and benzene-containing aromatics.

[0010] As a further preferred embodiment of the present invention, the carbon-free atmosphere is any one of oxygen, argon, nitrogen, ammonia, hydrogen, sulfur-containing gas without carbon, chlorine-containing gas without carbon, boron-containing gas without carbon, selenium-containing gas without carbon, fluorine-containing gas without carbon, bromine-containing gas without carbon, iodine-containing gas without carbon, and phosphorus-containing gas without carbon.

[0011] Preferably, the boron-containing gas that does not contain carbon is sulfur dioxide, and the phosphorus-containing gas that does not contain carbon is phosphine.

[0012] As a further preferred embodiment of the present invention, the power of the first plasma treatment is 100W to 300W, and the treatment time is 10min to 120min;

[0013] Preferably, the power of the first plasma treatment is 150W to 270W, and the treatment time is 30min to 100min.

[0014] As a further preferred embodiment of the present invention, the power of the second plasma treatment is 100W to 300W, and the treatment time is 10min to 120min;

[0015] Preferably, the power of the second plasma treatment is 150W to 270W, and the treatment time is 30min to 100min.

[0016] As a further preferred embodiment of the present invention, both the first plasma treatment and the second plasma treatment are performed at room temperature.

[0017] As a further preferred embodiment of the present invention, the zinc anode without an artificial solid electrolyte interface film is a clean zinc sheet.

[0018] As a further preferred embodiment of the present invention, the contact angle of the zinc-ion battery negative electrode regulated by the artificial solid electrolyte interface film is 10° to 80°, and the thickness of the artificial solid electrolyte interface film is 5 μm to 20 μm; the symmetrical battery constructed using the zinc-ion battery negative electrode regulated by the artificial solid electrolyte interface film has a cycle time of 500 h to 3000 h; the assembled battery constructed using the zinc-ion battery negative electrode regulated by the artificial solid electrolyte interface film and a manganese dioxide positive electrode has a discharge capacity of 150 to 400 mAh g. -1 ;

[0019] Preferably, the contact angle of the zinc-ion battery negative electrode regulated by the artificial solid electrolyte interface film is 20° to 60°.

[0020] According to another aspect of the present invention, the present invention provides the application of the zinc-ion battery negative electrode regulated by the above-mentioned artificial solid electrolyte interface film as a zinc-ion battery electrode.

[0021] Preferred application is as the negative electrode of zinc-ion batteries.

[0022] As a further preferred embodiment of the present invention, the zinc-ion battery is an aqueous zinc-ion battery.

[0023] Compared with the prior art, the technical solution conceived in this invention artificially regulates the interface of the zinc anode by performing two plasma treatments in a specific atmosphere, forming an artificial solid electrolyte interface film to regulate the zinc-ion battery anode interface. This invention first pre-treats the zinc anode without an artificial solid electrolyte interface film in a first atmosphere (i.e., a carbon-containing atmosphere) plasma (i.e., first plasma treatment), obtaining a low-quality initial artificial solid electrolyte interface film-modified zinc anode. Then, it is post-treated (i.e., a second plasma treatment) in a second atmosphere (i.e., a carbon-free atmosphere) plasma. The carbon-containing atmosphere can be, for example, C1-C8 alkanes or benzene-containing aromatics. The corresponding raw materials can be liquids in addition to gases (when liquid, the gas can be introduced by bubbling with an inert gas). This invention builds upon the initial artificial solid electrolyte interface film-modified zinc anode obtained through single plasma treatment (which often suffers from poor electrolyte wettability, easy corrosion, dendrite formation, poor cycle performance, and low quality). Further post-treatment via plasma chemical bonding enhances electrolyte wettability, reduces corrosion, mitigates dendrite formation, and improves cycle performance. The resulting high-quality artificial solid electrolyte interface film-modified zinc anode is particularly suitable for aqueous zinc-ion batteries, significantly improving capacity and cycle performance.

[0024] This invention utilizes two high-energy plasma treatments to regulate a high-quality artificial solid electrolyte interface film. Traditional plasma-derived, low-quality initial artificial solid electrolyte interface films modified zinc anode electrolytes exhibit poor wettability, susceptibility to corrosion, dendrite formation, and poor cycle performance. Existing technologies also employ single-plasma treatment of zinc anodes, such as CF4 plasma treatment, which forms a carbon film and a small amount of ZnF2, achieving a uniform electric field and to some extent uniform ion deposition. However, the small amount of ZnF2 is insufficient to fully meet the requirements of zinc anodes (low ZnF2 content results in a weak uniform ion field). The products obtained from such single-plasma treatments cannot simultaneously achieve a uniform electric field and uniform ion deposition, leading to dendrite formation, poor cycle performance, low quality, and low discharge capacity and high impedance in assembled batteries with the positive electrode. In this invention, a dual-control strategy employing both carbon-containing and carbon-free plasma methods is used to form a composite interface with a conductive network coupled to uniform zinc ion deposition. This interface simultaneously provides a uniform electric field and a uniform ion field, further improving cycle performance and ensuring uniform Zn ion deposition on the zinc sheet during subsequent battery applications, thus suppressing dendrite formation. This invention first performs pretreatment using a first type of plasma, then performs post-treatment on the initially low-quality artificial solid electrolyte interface film modified with a metallic zinc anode, thereby introducing a high-quality artificial solid electrolyte interface film. The second plasma treatment in this invention further modifies the already modified initially low-quality artificial electrolyte interface film using a plasma strategy. Through different electrochemical high-energy ion coupling strategies, high-performance zinc-ion battery anode materials can be obtained.

[0025] The zinc anode obtained by this invention (i.e., the interface-modified zinc anode) is a fast, efficient zinc anode with a directional control strategy, and can be applied to aqueous zinc-ion batteries, which can significantly improve the capacity, rate performance and cycle performance of zinc-ion batteries.

[0026] Furthermore, the processing method of this invention can be carried out at room temperature, reducing the economic cost pressure from temperature and expensive equipment, and facilitating industrialization. In addition, the method of this invention is simple to operate, has a short production cycle, low preparation cost, and meets the requirements of industrial production. The processing method of this invention can be carried out in the same plasma device. For example, after cleaning the zinc negative electrode, it can be placed in the plasma device. First, a first gas is introduced into the plasma device for the first plasma treatment, and then a second gas is introduced into the plasma device for the second plasma treatment. The entire process is carried out at room temperature.

[0027] Specifically, the present invention has the following beneficial effects:

[0028] 1. This invention uses carbon-containing atmosphere plasma to construct the initial artificial solid electrolyte interface film, which will not damage the original properties of the material itself. After appropriate carbon-containing gas plasma treatment, the original structure of the raw material can still be maintained, and the constructed carbon-containing interface can improve electron homogenization.

[0029] 2. The present invention uses carbon-free atmosphere plasma to further post-process the artificial solid electrolyte interface film, which ensures the initial interface electron homogenization. After appropriate carbon-free gas plasma post-processing, the original carbon-containing structure of the raw material can still be maintained, and the constructed interface can improve electron homogenization and ion homogenization.

[0030] 3. The atmosphere sources involved in this invention are wide-ranging, highly adaptable, and have good compatibility, resulting in high economic value and benefits.

[0031] 4. In particular, the present invention can adopt a room temperature gas plasma strategy, which is more convenient, has lower energy consumption, and lower cost compared with the existing high temperature synthesis process.

[0032] 5. The process of this invention is simple to operate, has a short cycle, and low cost, meeting the requirements of industrial production.

[0033] 6. This invention, through precise selection of the atmosphere and targeted control of the processing sequence, delves into plasma strategies, regulates the interfacial ion transport process, reduces dendrites, and greatly improves the cycle stability of the zinc anode. This invention overcomes the inherent limitations of traditional zinc anode interface modification by utilizing secondary plasma treatment and simultaneously controlling the zinc anode interface, achieving both electronic and ion homogenization, through the plasma atmosphere.

[0034] In summary, this invention utilizes a strategy of adjusting the atmosphere through secondary plasma treatment to control the interface structure and composition, resulting in a high-quality zinc anode modified with an artificial solid electrolyte interface film. By using this artificial solid electrolyte interface film to regulate the zinc-ion battery anode interface, the wettability of the electrolyte can be improved, the corrosion process of the zinc anode can be reduced, dendrite formation can be alleviated, and the cycle performance of the zinc anode can be enhanced. This, to a certain extent, accelerates the practical application of zinc-ion battery electrodes and promotes the widespread application of zinc-ion batteries. Attached Figure Description

[0035] Figure 1 This is a scanning electron microscope image of the zinc metal anode interface without plasma treatment provided in Comparative Example 1 of the present invention.

[0036] Figure 2 This is a scanning electron microscope image of the zinc metal anode interface without plasma post-treatment provided in Comparative Example 2 of the present invention.

[0037] Figure 3Scanning electron microscope (SEM) images of the zinc anode interface before and after carbon tetrafluoride / oxygen plasma treatment provided in Embodiment 1 of the present invention (A / B plasma pretreatment, representing plasma pretreatment in atmosphere A and plasma posttreatment in atmosphere B, the same below).

[0038] Figure 4 This is a scanning electron microscope image of the zinc anode interface before and after methane / nitrogen plasma treatment provided in Example 2 of the present invention.

[0039] Figure 5 This is a scanning electron microscope image of the zinc anode interface before and after ethane / hydrogen plasma treatment provided in Example 3 of the present invention.

[0040] Figure 6 This is a scanning electron microscope image of the zinc anode interface before and after propane / argon plasma treatment provided in Example 4 of the present invention.

[0041] Figure 7 This is a scanning electron microscope image of the butane / ammonia plasma pre- and post-treatment zinc anode interface provided in Example 5 of the present invention.

[0042] Figure 8 This is a scanning electron microscope image of the zinc anode interface before and after pentane / sulfur dioxide gas plasma treatment provided in Example 6 of the present invention.

[0043] Figure 9 The image shows the cycle performance of a symmetrical battery assembled with a zinc metal anode without plasma treatment, as provided in Comparative Example 1 of the present invention.

[0044] Figure 10 The image shows the cycle performance of a symmetrical battery assembled with a zinc metal anode without plasma post-treatment, as provided in Comparative Example 2 of this invention.

[0045] Figure 11 The cycling performance diagram is shown for the symmetrical battery assembled with a zinc anode after carbon tetrafluoride / oxygen plasma pre- and post-treatment provided in Embodiment 1 of the present invention.

[0046] Figure 12 Cyclic performance diagram of the symmetrical battery assembled with a zinc anode without post-treatment plasma provided in Comparative Example 4 of this invention.

[0047] Figure 13 The cycling performance diagram is shown for the symmetrical battery assembled with a zinc metal anode after methane / nitrogen plasma pre- and post-treatment provided in Example 2 of this invention.

[0048] Figure 14 The image shows the cycle performance of a symmetrical battery assembled with a zinc anode and ethane / hydrogen plasma pre- and post-treatment process, as provided in Example 3 of this invention.

[0049] Figure 15The circuit performance diagram is shown for the symmetrical battery assembled with a zinc metal anode after propane / argon plasma pre- and post-treatment provided in Example 4 of this invention.

[0050] Figure 16 The diagram shows the cycle stability of a zinc-ion battery assembled with commercial manganese dioxide and a zinc anode without plasma treatment, as provided in Comparative Example 1 of the present invention.

[0051] Figure 17 The image shows the cycle stability of a zinc-ion battery assembled with a zinc anode without plasma post-treatment and commercial manganese dioxide, as provided in Comparative Example 2 of this invention.

[0052] Figure 18 The diagram shows the cycle stability of a zinc-ion battery assembled with a carbon tetrafluoride / oxygen plasma pre- and post-treatment zinc anode and commercial manganese dioxide, as provided in Example 1 of this invention.

[0053] Figure 19 The diagram shows the capacity performance of a zinc-ion battery assembled with a zinc anode without plasma treatment and commercial manganese dioxide, as provided in Comparative Example 1 of the present invention.

[0054] Figure 20 The capacity performance diagram shows the zinc-ion battery assembled with commercial manganese dioxide and a metallic zinc anode without plasma post-treatment provided in Comparative Example 2 of the present invention.

[0055] Figure 21 The diagram shows the capacity performance of a zinc-ion battery assembled with a carbon tetrafluoride / oxygen plasma pre- and post-treatment zinc anode and commercial manganese dioxide, as provided in Example 1 of this invention.

[0056] Figure 22 Impedance diagram of a symmetrical battery assembled with a zinc metal anode without plasma treatment, provided in Comparative Example 1 of the present invention.

[0057] Figure 23 Impedance diagram of a symmetrical battery assembled with a zinc metal anode without plasma post-treatment, provided in Comparative Example 2 of the present invention.

[0058] Figure 24 Impedance diagram of a symmetrical battery assembled with a zinc anode after carbon tetrafluoride / oxygen plasma pre- and post-treatment, as provided in Embodiment 1 of the present invention. Detailed Implementation

[0059] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0060] The following examples and comparative examples were all conducted at room temperature.

[0061] Example 1

[0062] Preparation of the zinc anode interface before and after carbon tetrafluoride / oxygen plasma pretreatment:

[0063] (1) Cleaning of zinc metal: First, the 100μm thick zinc sheet, which has been cleaned with deionized water, acetone and alcohol, is vacuum dried to remove surface contaminants and then placed in a plasma device.

[0064] (2) Plasma pretreatment: Introduce carbon tetrafluoride: In the plasma equipment, under the atmosphere of carbon tetrafluoride, treat for 60 minutes with a power of 270W, and wait for the plasma equipment to cool down.

[0065] (3) Plasma post-treatment: Introduce oxygen: In the plasma equipment, under an oxygen atmosphere, process for 30 minutes at a power of 150W, and wait for the plasma equipment to cool down.

[0066] (4) Electrode performance test: The modified zinc anode prepared in Example 1 was applied to a symmetrical cell, as follows:

[0067] The modified zinc electrode obtained in Example 1 was placed in the positive electrode shell, and then a Whatman membrane was placed on top of the modified zinc electrode. 100 μL of electrolyte (i.e., a 2M ZnSO4 aqueous solution; the same applies below) was then added to the membrane, followed by another modified zinc electrode obtained in Example 1. Finally, a gasket and a negative electrode shell were added, and the battery was pressed into a button cell under a pressure of 10 MPa. The tested current density was 1 mA cm⁻¹. -2 The tested surface capacity is 1mAh cm⁻¹ -2 .

[0068] The modified zinc obtained in Example 1 was used as the negative electrode. Commercial manganese dioxide (as the positive electrode active material), polyvinylidene fluoride (PVDF), and conductive carbon black were mixed evenly at a mass ratio of 8:1:1. An appropriate amount of NMP was added to make a slurry (i.e., the active material), which was then coated onto a 13 mm diameter stainless steel foil current collector. After the solvent evaporated, the slurry was dried in a vacuum drying oven at 120 °C for 10 h. Then, the stainless steel foil coated with the active material was used as the working electrode and assembled into a coin cell zinc-ion battery with an aqueous electrolyte (i.e., a 2 M ZnSO4 aqueous solution; the same below). Charge and discharge tests were conducted, with a current density of 0.1 A / g (the same below) and a voltage range of 0.8-1.85 V.

[0069] The zinc anode prepared in step (3) of Example 1 was characterized by scanning electron microscopy, and the results are as follows: Figure 3 As shown, it can be seen that the puncture marks on the surface of the zinc metal negative electrode during production and processing have decreased significantly, the metal surface tends to be flat, there are no uneven areas, and the color is uniform.

[0070] Symmetrical battery data such as Figure 11 As shown, the zinc anode prepared in step (3) of Example 1 fails after 2100 hours. The cycle performance is significantly improved compared to Comparative Examples 1 to 5 below.

[0071] The cycle stability diagram of the zinc-ion battery assembled with the zinc anode obtained in step (3) of Example 1 and commercial manganese dioxide is shown below. Figure 18 As shown, the capacity retention rate was 79.3%, which is a significant improvement compared to Comparative Examples 1 to 5.

[0072] The charge-discharge curves of the zinc-ion battery assembled with the zinc anode obtained in step (3) of Example 1 and commercial manganese dioxide are shown in the figure. Figure 21 As shown, the capacity is 189.7 mAh g. -1 Compared to Comparative Examples 1 to 5, the discharge capacity is superior.

[0073] The AC impedance diagram of the symmetrical battery assembled with the zinc metal negative electrode obtained in step (3) of Example 1 is as follows: Figure 24 As shown, the charge transfer impedance is 539Ω, which is an improvement in conductivity compared to Comparative Examples 1 to 5.

[0074] Comparative Example 1

[0075] Plasma-free treatment: Zinc metal anode testing:

[0076] (1) Cleaning of zinc metal: First, the 100μm thick zinc sheet, which has been cleaned with deionized water, acetone and alcohol, is vacuum dried to remove surface contaminants.

[0077] (2) Electrode performance test: The zinc sheet obtained in Comparative Example 1 was used as the negative electrode in a symmetrical battery, as follows:

[0078] The zinc sheet electrode obtained in Comparative Example 1 was placed in the positive electrode shell, and then a Whatman separator was placed on top of the modified zinc sheet electrode. 100 μL of electrolyte was then added to the separator, followed by another zinc sheet electrode obtained in Comparative Example 1. Finally, a gasket and a negative electrode shell were added, and the battery was pressed into a button cell under a pressure of 10 MPa. The tested current density was 1 mA cm⁻¹. -2 The tested surface capacity is 1mAh cm. -2 .

[0079] Using the zinc obtained in Comparative Example 1 as the negative electrode, commercial manganese dioxide, polyvinylidene fluoride (PVDF), and conductive carbon black were mixed evenly at a mass ratio of 8:1:1. An appropriate amount of NMP was added to prepare a slurry (i.e., the active material), which was then coated onto a 13 mm diameter stainless steel foil. After the solvent evaporated, the foil was placed in a vacuum drying oven and dried at 120 °C for 10 h. Then, the stainless steel foil coated with the active material was used as the working electrode and assembled with an aqueous electrolyte to form a coin cell zinc-ion battery for charge-discharge testing. The voltage range was 0.8-1.85 V.

[0080] The zinc anode prepared in step (1) of Comparative Example 1 was characterized by scanning electron microscopy, and the results are as follows: Figure 1 As shown, the surface of the zinc metal anode has traces left from the typical metal processing production process of commercial zinc metal anodes.

[0081] Symmetrical battery data such as Figure 9 As shown, the zinc anode prepared in step (1) of Comparative Example 1 fails after 55 hours, showing poor cycle performance.

[0082] Comparative analysis of the cycle stability diagrams of the zinc anode prepared in step (1) of Example 1 and the zinc-ion battery assembled with commercial manganese dioxide is shown below. Figure 16 As shown, the capacity retention rate is 53.4%, which is relatively poor.

[0083] The charge-discharge curves of the zinc anode prepared in step (1) of Example 1 and the zinc-ion battery assembled with commercial manganese dioxide are shown below. Figure 19 As shown, the capacity is 97mAh g -1 It has a low capacity.

[0084] The AC impedance diagram of the symmetrical battery assembled with the zinc metal negative electrode obtained in step (1) of Example 1 is shown below. Figure 22 As shown, the charge transfer impedance is 1500Ω, indicating poor conductivity.

[0085] Comparative Example 2

[0086] Preparation of the zinc anode interface without post-treatment: carbon tetrafluoride plasma treatment

[0087] (1) Cleaning of zinc metal: First, the 100μm thick zinc sheet, which has been cleaned with deionized water, acetone and alcohol, is vacuum dried to remove surface contaminants and then placed in a plasma device.

[0088] (2) Plasma pretreatment: Introduce carbon tetrafluoride: In the plasma equipment, under the atmosphere of carbon tetrafluoride, treat for 60 minutes with a power of 270W, and wait for the plasma equipment to cool down.

[0089] (3) Electrode performance test: The modified zinc metal anode prepared in Comparative Example 2 was applied to a symmetrical battery, as follows:

[0090] The modified zinc electrode obtained in Comparative Example 2 was placed in the positive electrode shell, and then a Whatman membrane was placed on top of the modified zinc electrode. 100 μL of electrolyte was then added to the membrane, followed by another modified zinc electrode obtained in Comparative Example 2. Finally, a gasket and a negative electrode shell were added, and the battery was pressed into a button cell under a pressure of 10 MPa. The tested current density was 1 mA cm⁻¹. -2 The tested surface capacity is 1mAh cm. -2 .

[0091] Using the modified zinc obtained in Comparative Example 2 as the negative electrode, commercial manganese dioxide, polyvinylidene fluoride (PVDF), and conductive carbon black were mixed evenly at a mass ratio of 8:1:1. An appropriate amount of NMP was added to prepare a slurry (i.e., the active material), which was then coated onto a 13 mm diameter stainless steel foil. After the solvent evaporated, the foil was placed in a vacuum drying oven and dried at 120 °C for 10 h. Then, the stainless steel foil coated with the active material was used as the working electrode and assembled with an aqueous electrolyte to form a coin cell zinc-ion battery for charge-discharge testing. The voltage range was 0.8-1.85 V.

[0092] The zinc anode prepared in step (2) of Comparative Example 2 was characterized by scanning electron microscopy, and the results are as follows: Figure 2 As shown, it can be seen that the dents on the surface of the zinc metal negative electrode during production and processing are reduced, and the metal surface tends to be flat. However, it is obvious that there are uneven bright white parts in some areas.

[0093] Symmetrical battery data such as Figure 10 As shown, the zinc anode prepared in step (2) of Comparative Example 2 fails after 130 hours. The cycle performance is improved compared to Comparative Example 1, but not significantly.

[0094] Comparative analysis of the cycle stability diagrams of the zinc anode prepared in step (2) of Example 2 and the zinc-ion battery assembled with commercial manganese dioxide is shown below. Figure 17 As shown, the capacity retention rate is 76.4%, which is an improvement compared to Comparative Example 1.

[0095] The charge-discharge curves of the zinc anode prepared in step (2) of Example 2 and the zinc-ion battery assembled with commercial manganese dioxide are shown below. Figure 20 As shown, the capacity is 158mAh g -1 Compared to Comparative Example 1, the capacity is improved to some extent.

[0096] The AC impedance diagram of the symmetrical battery assembled with the zinc metal negative electrode obtained in step (2) of Example 2 is shown below. Figure 23 As shown, the charge transfer impedance is 924Ω, which is an improvement in conductivity compared to Comparative Example 1.

[0097] Comparative Example 3

[0098] Preparation of zinc anode interface without pretreatment: oxygen plasma treatment

[0099] (1) Cleaning of zinc metal: First, the 100μm thick zinc sheet, which has been cleaned with deionized water, acetone and alcohol, is vacuum dried to remove surface contaminants and then placed in a plasma device.

[0100] (2) Plasma pretreatment: oxygen is introduced: in the plasma equipment, under an oxygen atmosphere, the plasma is treated with a power of 150W for 30 minutes, and then the plasma equipment is allowed to cool down.

[0101] (3) Electrode performance test: The modified zinc metal anode prepared in Comparative Example 3 was applied to a symmetrical cell, as follows:

[0102] The modified zinc electrode obtained in Comparative Example 3 was placed in the positive electrode shell, and then a Whatman membrane was placed on top of the modified zinc electrode. 100 μL of electrolyte was then added to the membrane, followed by another modified zinc electrode obtained in Comparative Example 3. Finally, a gasket and a negative electrode shell were added, and the battery was pressed into a button cell under a pressure of 10 MPa. The tested current density was 1 mA cm⁻¹. -2 The tested surface capacity is 1mAh cm. -2 .

[0103] Using the modified zinc obtained in Comparative Example 3 as the negative electrode, commercial manganese dioxide, polyvinylidene fluoride (PVDF), and conductive carbon black were mixed evenly at a mass ratio of 8:1:1. An appropriate amount of NMP was added to prepare a slurry (i.e., the active material), which was then coated onto a 13 mm diameter stainless steel foil. After the solvent evaporated, the foil was placed in a vacuum drying oven and dried at 120 °C for 10 h. Then, the stainless steel foil coated with the active material was used as the working electrode and assembled with an aqueous electrolyte to form a coin cell zinc-ion battery for charge-discharge testing. The voltage range was 0.8-1.85 V.

[0104] Example 2

[0105] Preparation of the zinc anode interface before and after methane / nitrogen plasma pretreatment:

[0106] (1) Cleaning of zinc metal: First, the 100μm thick zinc sheet, which has been cleaned with deionized water, acetone and alcohol, is vacuum dried to remove surface contaminants and then placed in a plasma device.

[0107] (2) Plasma pretreatment: Methane is introduced: In the plasma equipment, under a methane atmosphere, the plasma is treated with a power of 200W for 100 minutes, and then the plasma equipment is allowed to cool down.

[0108] (3) Plasma post-treatment: Nitrogen gas is introduced: In the plasma equipment, under a nitrogen atmosphere, the plasma is treated with a power of 180W for 30 minutes, and then the plasma equipment is allowed to cool down.

[0109] (4) Electrode performance test: The modified zinc anode prepared in Example 2 was applied to a symmetrical cell, as follows:

[0110] The modified zinc electrode obtained in Example 2 was placed in the positive electrode shell, and then a Whatman membrane was placed on top of the modified zinc electrode. 100 μL of electrolyte was then added to the membrane, followed by another modified zinc electrode obtained in Example 2. Finally, a gasket and a negative electrode shell were added, and the battery was pressed into a button cell under a pressure of 10 MPa. The tested current density was 1 mA cm⁻¹. -2 The tested surface capacity is 1mAh cm. -2 .

[0111] Using the modified zinc obtained in Example 2 as the negative electrode, commercial manganese dioxide, polyvinylidene fluoride (PVDF), and conductive carbon black were mixed evenly at a mass ratio of 8:1:1. An appropriate amount of NMP was added to make a slurry (i.e., the active material), which was then coated onto a 13 mm diameter stainless steel foil. After the solvent evaporated, the foil was placed in a vacuum drying oven and dried at 120 °C for 10 h. Then, the stainless steel foil coated with the active material was used as the working electrode and assembled with an aqueous electrolyte to form a coin cell zinc-ion battery for charge-discharge testing. The voltage range was 0.8-1.85 V.

[0112] The zinc anode prepared in step (3) of Example 2 was characterized by scanning electron microscopy, and the results are as follows: Figure 4 As shown, there are no puncture marks on the surface of the zinc metal anode, the introduction of the interface modification layer is obvious, and the modification layer is porous, which is conducive to ion transport.

[0113] Symmetrical battery data such as Figure 13 As shown, the zinc anode prepared in step (3) of Example 2 fails after 1250 hours, and the cycle performance is significantly improved.

[0114] Comparative Example 4

[0115] Preparation of the zinc anode interface without post-processing: methane plasma treatment

[0116] (1) Cleaning of zinc metal: First, the 100μm thick zinc sheet, which has been cleaned with deionized water, acetone and alcohol, is vacuum dried to remove surface contaminants and then placed in a plasma device.

[0117] (2) Plasma pretreatment: Methane is introduced: In the plasma equipment, under a methane atmosphere, the plasma is treated with a power of 200W for 100 minutes, and then the plasma equipment is allowed to cool down.

[0118] (3) Electrode performance test: The modified zinc anode prepared in Comparative Example 4 was applied to a symmetrical cell, as follows:

[0119] The modified zinc electrode obtained in Comparative Example 4 was placed in the positive electrode shell, and then a Whatman membrane was placed on top of the modified zinc electrode. 100 μL of electrolyte was then added to the membrane, followed by another modified zinc electrode obtained in Comparative Example 4. Finally, a gasket and a negative electrode shell were added, and the battery was pressed into a button cell under a pressure of 10 MPa. The tested current density was 1 mA cm⁻¹. -2 The tested surface capacity is 1mAh cm. -2 .

[0120] Using the modified zinc obtained in Comparative Example 4 as the negative electrode, commercial manganese dioxide, polyvinylidene fluoride (PVDF), and conductive carbon black were mixed evenly at a mass ratio of 8:1:1. An appropriate amount of NMP was added to prepare a slurry (i.e., the active material), which was then coated onto a 13 mm diameter stainless steel foil. After the solvent evaporated, the foil was placed in a vacuum drying oven and dried at 120 °C for 10 h. Then, the stainless steel foil coated with the active material was used as the working electrode and assembled with an aqueous electrolyte to form a coin cell zinc-ion battery for charge-discharge testing. The voltage range was 0.8-1.85 V.

[0121] Symmetrical battery data such as Figure 12As shown, the zinc anode prepared in step (2) of Comparative Example 4 fails after 250 hours, exhibiting poor cycle performance.

[0122] Comparative Example 5

[0123] Preparation of the zinc anode interface without pretreatment: Nitrogen plasma treatment

[0124] (1) Cleaning of zinc metal: First, the 100μm thick zinc sheet, which has been cleaned with deionized water, acetone and alcohol, is vacuum dried to remove surface contaminants and then placed in a plasma device.

[0125] (2) Plasma pretreatment: Methane is introduced: In the plasma equipment, under a methane atmosphere, the plasma is treated at a power of 180W for 30 minutes, and then the plasma equipment is allowed to cool down.

[0126] (3) Electrode performance test: The modified zinc anode prepared in Comparative Example 5 was applied to a symmetrical cell, as follows:

[0127] The modified zinc electrode obtained in Comparative Example 5 was placed in the positive electrode shell, and then a Whatman membrane was placed on top of the modified zinc electrode. 100 μL of electrolyte was then added to the membrane, followed by another modified zinc electrode obtained in Comparative Example 5. Finally, a gasket and a negative electrode shell were added, and the battery was pressed into a button cell under a pressure of 10 MPa. The tested current density was 1 mA cm⁻¹. -2 The tested surface capacity is 1mAh cm. -2 .

[0128] Using the modified zinc obtained in Comparative Example 5 as the negative electrode, commercial manganese dioxide, polyvinylidene fluoride (PVDF), and conductive carbon black were mixed evenly at a mass ratio of 8:1:1. An appropriate amount of NMP was added to prepare a slurry (i.e., the active material), which was then coated onto a 13 mm diameter stainless steel foil. After the solvent evaporated, the foil was placed in a vacuum drying oven and dried at 120 °C for 10 h. Then, the stainless steel foil coated with the active material was used as the working electrode and assembled with an aqueous electrolyte to form a coin cell zinc-ion battery for charge-discharge testing. The voltage range was 0.8-1.85 V.

[0129] Example 3

[0130] Preparation of the zinc anode interface before and after ethane / hydrogen plasma pretreatment:

[0131] (1) Cleaning of zinc metal: First, the 100μm thick zinc sheet, which has been cleaned with deionized water, acetone and alcohol, is vacuum dried to remove surface contaminants and then placed in a plasma device.

[0132] (2) Plasma pretreatment: Ethane is introduced: In the plasma equipment, under an ethane atmosphere, the plasma is treated with a power of 200W for 100 minutes, and then the plasma equipment is allowed to cool down.

[0133] (3) Plasma post-treatment: Hydrogen gas is introduced: In the plasma equipment, under the hydrogen atmosphere, the plasma is treated with a power of 180W for 30 minutes, and then the plasma equipment is allowed to cool down.

[0134] (4) Electrode performance test: The modified zinc anode prepared in Example 3 was applied to a symmetrical cell, as follows:

[0135] The modified zinc electrode obtained in Example 3 was placed in the positive electrode shell, and then a Whatman membrane was placed on top of the modified zinc electrode. 100 μL of electrolyte was then added to the membrane, followed by another modified zinc electrode obtained in Example 3. Finally, a gasket and a negative electrode shell were added, and the battery was pressed into a button cell under a pressure of 10 MPa. The tested current density was 1 mA cm⁻¹. -2 The tested surface capacity is 1mAh cm. -2 .

[0136] Using the modified zinc obtained in Example 3 as the negative electrode, commercial manganese dioxide, polyvinylidene fluoride (PVDF), and conductive carbon black were mixed evenly at a mass ratio of 8:1:1. An appropriate amount of NMP was added to make a slurry (i.e., the active material), which was then coated onto a 13 mm diameter stainless steel foil. After the solvent evaporated, the foil was placed in a vacuum drying oven and dried at 120 °C for 10 h. Then, the stainless steel foil coated with the active material was used as the working electrode and assembled with an aqueous electrolyte to form a coin cell zinc-ion battery for charge-discharge testing. The voltage range was 0.8-1.85 V.

[0137] The zinc anode prepared in step (3) of Example 3 was characterized by scanning electron microscopy, and the results are as follows: Figure 5 As shown, the introduction of the interface modification layer on the surface of the zinc metal anode is obvious. The modification layer is porous, which is conducive to ion transport.

[0138] Symmetrical battery data such as Figure 14 As shown, the zinc anode prepared in step (3) of Example 3 fails after 2500 hours, and the cycle performance is significantly improved.

[0139] Example 4

[0140] Preparation of the zinc anode interface before and after propane / argon plasma pretreatment:

[0141] (1) Cleaning of zinc metal: First, the 100μm thick zinc sheet, which has been cleaned with deionized water, acetone and alcohol, is vacuum dried to remove surface contaminants and then placed in a plasma device.

[0142] (2) Plasma pretreatment: Propane is introduced: In the plasma equipment, under a propane atmosphere, the plasma is treated with a power of 150W for 30 minutes, and then the plasma equipment is allowed to cool down.

[0143] (3) Plasma post-treatment: Argon gas is introduced: In the plasma equipment, under the atmosphere of argon, the plasma is treated with a power of 270W for 100 minutes, and then the plasma equipment is allowed to cool down.

[0144] (4) Electrode performance test: The modified zinc metal anode prepared in Example 4 was applied to a symmetrical cell, as follows:

[0145] The modified zinc electrode obtained in Example 4 was placed in the positive electrode shell, and then a Whatman membrane was placed on top of the modified zinc electrode. 100 μL of electrolyte was then added to the membrane, followed by another modified zinc electrode obtained in Example 4. Finally, a gasket and a negative electrode shell were added, and the battery was pressed into a button cell under a pressure of 10 MPa. The tested current density was 1 mA cm⁻¹. -2 The tested surface capacity is 1mAh cm. -2 .

[0146] Using the modified zinc obtained in Example 4 as the negative electrode, commercial manganese dioxide, polyvinylidene fluoride (PVDF), and conductive carbon black were mixed evenly at a mass ratio of 8:1:1. An appropriate amount of NMP was added to make a slurry (i.e., the active material), which was then coated onto a 13 mm diameter stainless steel foil. After the solvent evaporated, the foil was placed in a vacuum drying oven and dried at 120 °C for 10 h. Then, the stainless steel foil coated with the active material was used as the working electrode and assembled with an aqueous electrolyte to form a coin cell zinc-ion battery for charge-discharge testing. The voltage range was 0.8-1.85 V.

[0147] The zinc anode prepared in step (3) of Example 4 was characterized by scanning electron microscopy, and the results are as follows: Figure 6 As shown, the introduction of the interface modification layer on the surface of the zinc metal anode is obvious. The modification layer is porous, which is conducive to ion transport.

[0148] Symmetrical battery data such as Figure 15 As shown, the zinc anode prepared in step (3) of Example 4 fails after 2880 hours, and the cycle performance is significantly improved.

[0149] Example 5

[0150] Preparation of the zinc anode interface before and after plasma treatment with butane / ammonia:

[0151] (1) Cleaning of zinc metal: First, the 100μm thick zinc sheet, which has been cleaned with deionized water, acetone and alcohol, is vacuum dried to remove surface contaminants and then placed in a plasma device.

[0152] (2) Plasma pretreatment: Butane is introduced: In the plasma equipment, under the butane atmosphere, it is treated with a power of 200W for 50 minutes, and the plasma equipment is allowed to cool down.

[0153] (3) Plasma post-treatment: Ammonia gas is introduced: In the plasma equipment, under the atmosphere of ammonia, the plasma is treated with a power of 200W for 60 minutes, and then the plasma equipment is allowed to cool down.

[0154] (4) Electrode performance test: The modified zinc anode prepared in Example 5 was applied to a symmetrical cell, as follows:

[0155] The modified zinc electrode obtained in Example 5 was placed in the positive electrode shell, and then a Whatman membrane was placed on top of the modified zinc electrode. 100 μL of electrolyte was then added to the membrane, followed by another modified zinc electrode obtained in Example 5. Finally, a gasket and a negative electrode shell were added, and the battery was pressed into a button cell under a pressure of 10 MPa. The tested current density was 1 mA cm⁻¹. -2 The tested surface capacity is 1mAh cm. -2 .

[0156] Using the modified zinc obtained in Example 5 as the negative electrode, commercial manganese dioxide, polyvinylidene fluoride (PVDF), and conductive carbon black were mixed evenly at a mass ratio of 8:1:1. An appropriate amount of NMP was added to make a slurry (i.e., the active material), which was then coated onto a 13 mm diameter stainless steel foil. After the solvent evaporated, the foil was placed in a vacuum drying oven and dried at 120 °C for 10 h. Then, the stainless steel foil coated with the active material was used as the working electrode and assembled with an aqueous electrolyte to form a coin cell zinc-ion battery for charge-discharge testing. The voltage range was 0.8-1.85 V.

[0157] The zinc anode prepared in step (3) of Example 5 was characterized by scanning electron microscopy, and the results are as follows: Figure 7 As shown, the introduction of the interface modification layer on the surface of the zinc metal anode is obvious. The modification layer is porous, which is conducive to ion transport.

[0158] Example 6

[0159] Preparation of the pentane / sulfur dioxide plasma pre- and post-treatment interface for zinc anode:

[0160] (1) Cleaning of zinc metal: First, the 100μm thick zinc sheet, which has been cleaned with deionized water, acetone and alcohol, is vacuum dried to remove surface contaminants and then placed in a plasma device.

[0161] (2) Plasma pretreatment: Pentane is introduced: In the plasma equipment, under the pentane atmosphere, the plasma is treated with a power of 220W for 40 minutes, and then the plasma equipment is cooled down.

[0162] (3) Plasma post-treatment: Sulfur dioxide gas is introduced: In the plasma equipment, under the atmosphere of sulfur dioxide gas, the plasma is treated with a power of 170W for 80 minutes, and then the plasma equipment is allowed to cool down.

[0163] (4) Electrode performance test: The modified zinc anode prepared in Example 6 was applied to a symmetrical cell, as follows:

[0164] The modified zinc electrode obtained in Example 6 was placed in the positive electrode shell, and then a Whatman membrane was placed on top of the modified zinc electrode. 100 μL of electrolyte was then added to the membrane, followed by another modified zinc electrode obtained in Example 6. Finally, a gasket and a negative electrode shell were added, and the battery was pressed into a button cell under a pressure of 10 MPa. The tested current density was 1 mA cm⁻¹. -2 The tested surface capacity is 1mAh cm. -2 .

[0165] Using the modified zinc obtained in Example 6 as the negative electrode, commercial manganese dioxide, polyvinylidene fluoride (PVDF), and conductive carbon black were mixed evenly at a mass ratio of 8:1:1. An appropriate amount of NMP was added to make a slurry (i.e., the active material), which was then coated onto a 13 mm diameter stainless steel foil. After the solvent evaporated, the foil was placed in a vacuum drying oven and dried at 120 °C for 10 h. Then, the stainless steel foil coated with the active material was used as the working electrode and assembled with an aqueous electrolyte to form a coin cell zinc-ion battery for charge-discharge testing. The voltage range was 0.8-1.85 V.

[0166] The zinc anode prepared in step (3) of Example 6 was characterized by scanning electron microscopy, and the results are as follows: Figure 8 As shown, the introduction of the interface modification layer on the surface of the zinc metal anode is obvious. The modification layer is porous, which is conducive to ion transport.

[0167] Example 7

[0168] Preparation of the zinc anode interface before and after cyclohexane / phosphine plasma pretreatment:

[0169] (1) Cleaning of zinc metal: First, the 100μm thick zinc sheet, which has been cleaned with deionized water, acetone and alcohol, is vacuum dried to remove surface contaminants and then placed in a plasma device.

[0170] (2) Plasma pretreatment: Cyclohexane is introduced: In the plasma equipment, under a cyclohexane atmosphere, the plasma is treated with a power of 180W for 70 minutes, and then the plasma equipment is allowed to cool down.

[0171] (3) Plasma post-treatment: Phosphine gas is introduced: In the plasma equipment, under the atmosphere of phosphine gas, the plasma is treated with a power of 210W for 40 minutes, and then the plasma equipment is allowed to cool down.

[0172] (4) Electrode performance test: The modified zinc metal anode prepared in Example 7 was applied to a symmetrical cell, as follows:

[0173] The modified zinc electrode obtained in Example 7 was placed in the positive electrode shell, and then a Whatman membrane was placed on top of the modified zinc electrode. 100 μL of electrolyte was then added to the membrane, followed by another modified zinc electrode obtained in Example 7. Finally, a gasket and a negative electrode shell were added, and the battery was pressed into a button cell under a pressure of 10 MPa. The tested current density was 1 mA cm⁻¹. -2 The tested surface capacity is 1mAh cm. -2 .

[0174] Using the modified zinc obtained in Example 7 as the negative electrode, commercial manganese dioxide, polyvinylidene fluoride (PVDF), and conductive carbon black were mixed evenly at a mass ratio of 8:1:1. An appropriate amount of NMP was added to prepare a slurry (i.e., the active material), which was then coated onto a 13 mm diameter stainless steel foil. After the solvent evaporated, the foil was placed in a vacuum drying oven and dried at 120 °C for 10 h. Then, the stainless steel foil coated with the active material was used as the working electrode and assembled with an aqueous electrolyte to form a coin cell zinc-ion battery for charge-discharge testing. The voltage range was 0.8-1.85 V.

[0175] Example 8

[0176] Preparation of the zinc anode interface before and after plasma treatment with benzene / hydrogen sulfide:

[0177] (1) Cleaning of zinc metal: First, the 100μm thick zinc sheet, which has been cleaned with deionized water, acetone and alcohol, is vacuum dried to remove surface contaminants and then placed in a plasma device.

[0178] (2) Plasma pretreatment: Introduce benzene gas: In the plasma equipment, under the benzene atmosphere, treat for 60 minutes with a power of 170W, and wait for the plasma equipment to cool down.

[0179] (3) Plasma post-treatment: Introduce hydrogen sulfide gas: In the plasma equipment, under the atmosphere of hydrogen sulfide gas, process for 50 minutes with a power of 200W, and wait for the plasma equipment to cool down.

[0180] (4) Electrode performance test: The modified zinc metal anode prepared in Example 8 was applied to a symmetrical cell, as follows:

[0181] The modified zinc electrode obtained in Example 8 was placed in the positive electrode shell, and then a Whatman membrane was placed on top of the modified zinc electrode. 100 μL of electrolyte was then added to the membrane, followed by another modified zinc electrode obtained in Example 8. Finally, a gasket and a negative electrode shell were added, and the battery was pressed into a button cell under a pressure of 10 MPa. The tested current density was 1 mA cm⁻¹. -2 The tested surface capacity is 1mAh cm. -2 .

[0182] Using the modified zinc obtained in Example 8 as the negative electrode, commercial manganese dioxide, polyvinylidene fluoride (PVDF), and conductive carbon black were mixed evenly at a mass ratio of 8:1:1. An appropriate amount of NMP was added to make a slurry (i.e., the active material), which was then coated onto a 13 mm diameter stainless steel foil. After the solvent evaporated, the foil was placed in a vacuum drying oven and dried at 120 °C for 10 h. Then, the stainless steel foil coated with the active material was used as the working electrode and assembled with an aqueous electrolyte to form a coin cell zinc-ion battery for charge-discharge testing. The voltage range was 0.8-1.85 V.

[0183] The thickness and contact angle of the zinc anodes obtained by electron microscopy and optical microscopy in the above embodiments and comparative embodiments are shown in Table 1. The cycle performance results of symmetrical cells further assembled using the zinc anodes obtained in the embodiments and comparative embodiments are shown in Table 2. The capacity retention and capacity performance results of full cells assembled using the zinc anodes obtained in the embodiments and comparative embodiments and commercial manganese dioxide are shown in Table 3. The AC impedance results of symmetrical cells further assembled using the zinc anodes obtained in the embodiments and comparative embodiments are shown in Table 4.

[0184] Table 1. Thickness and contact angle of the artificial solid electrolyte interface film on the modified zinc anode.

[0185]

[0186]

[0187] Table 2 Cycle performance of symmetrical cells assembled with modified zinc anodes

[0188] name Time (h) Comparative Example 1 55 Comparative Example 2 130 Comparative Example 3 286 Example 1 2100 Comparative Example 4 250 Comparative Example 5 215 Example 2 1250 Example 3 2500 Example 4 2880 Example 5 3000 Example 6 500 Example 7 1100 Example 8 1860

[0189] Table 3. Capacity retention and capacity of full cells assembled with modified zinc anode and commercial manganese dioxide.

[0190]

[0191]

[0192] Table 4. AC impedance of the symmetrical cells assembled with the modified zinc anode.

[0193] name <![CDATA[R s (Oh)]]> <![CDATA[R ct (Oh)]]> Comparative Example 1 1.05 1500 Comparative Example 2 1.52 924 Comparative Example 3 1.03 984 Example 1 0.22 592 Comparative Example 4 1.76 762 Comparative Example 5 1.02 798 Example 2 0.83 532 Example 3 0.94 596 Example 4 0.31 614 Example 5 0.42 682 Example 6 0.55 649 Example 7 0.65 519 Example 8 0.57 571

[0194] As shown in Table 1, the thickness of the zinc anode in the interface film after two plasma modifications is higher than that in the film after a single modification, and the contact angle of the zinc anode in the interface film after two plasma modifications is lower than that in the film after a single modification.

[0195] As can be seen from Table 2, the cycling performance of the zinc anode was significantly improved after the two plasma-modified interfacial films.

[0196] As can be seen from Table 3, the capacity retention of the full cell assembled with zinc anode and commercial manganese dioxide was significantly improved after the two plasma-modified interface films.

[0197] As can be seen from Table 4, the AC impedance of the symmetrical cell assembled with zinc anode significantly decreased after the two plasma-modified interface films.

[0198] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A zinc-ion battery negative electrode regulated by an artificial solid electrolyte interface film, characterized in that, The zinc-ion battery anode controlled by the artificial solid electrolyte interface film is obtained by first placing a metallic zinc anode without an artificial solid electrolyte interface film in a plasma of a first atmosphere for a first plasma treatment, and then in a plasma of a second atmosphere for a second plasma treatment, thereby obtaining a zinc-ion battery anode with an artificial solid electrolyte interface film on its surface. The first atmosphere is a carbon-containing atmosphere, and the second atmosphere is a carbon-free atmosphere. The carbon-containing atmosphere is selected from C1-C8 alkanes and benzene-containing aromatics.

2. The zinc-ion battery negative electrode regulated by the artificial solid electrolyte interface film as described in claim 1, characterized in that, The carbon-free atmosphere is any one of oxygen, argon, nitrogen, ammonia, hydrogen, sulfur-containing gas without carbon, chlorine-containing gas without carbon, boron-containing gas without carbon, selenium-containing gas without carbon, fluorine-containing gas without carbon, bromine-containing gas without carbon, iodine-containing gas without carbon, and phosphorus-containing gas without carbon.

3. The zinc-ion battery negative electrode regulated by the artificial solid electrolyte interface film as described in claim 2, characterized in that, The boron-containing gas that does not contain carbon is sulfur dioxide, and the phosphorus-containing gas that does not contain carbon is phosphine.

4. The zinc-ion battery negative electrode regulated by the artificial solid electrolyte interface film as described in claim 1, characterized in that, The power of the first plasma treatment is 100 W to 300 W, and the treatment time is 10 min to 120 min.

5. The zinc-ion battery negative electrode regulated by the artificial solid electrolyte interface film as described in claim 4, characterized in that, The power of the first plasma treatment is 150 W to 270 W, and the treatment time is 30 min to 100 min.

6. The zinc-ion battery negative electrode regulated by the artificial solid electrolyte interface film as described in claim 1, characterized in that, The power of the second plasma treatment is 100 W to 300 W, and the treatment time is 10 min to 120 min.

7. The zinc-ion battery negative electrode regulated by the artificial solid electrolyte interface film as described in claim 6, characterized in that, The power of the second plasma treatment is 150 W to 270 W, and the treatment time is 30 min to 100 min.

8. The zinc-ion battery negative electrode regulated by the artificial solid electrolyte interface film as described in claim 1, characterized in that, Both the first plasma treatment and the second plasma treatment were performed at room temperature.

9. The zinc-ion battery negative electrode regulated by the artificial solid electrolyte interface film as described in claim 1, characterized in that, The zinc anode, which has no artificial solid electrolyte interface film, is a clean zinc sheet.

10. The zinc-ion battery negative electrode regulated by the artificial solid electrolyte interface film as described in claim 1, characterized in that, The contact angle of the negative electrode in a zinc-ion battery regulated by an artificial solid electrolyte interface film is 10°. o ~ 80 o The thickness of the artificial solid electrolyte interface film is 5 μm to 20 μm; the cycle time of the symmetrical battery constructed using the zinc-ion battery anode regulated by this artificial solid electrolyte interface film is 500 h to 3000 h; the discharge capacity of the assembled battery constructed using the zinc-ion battery anode regulated by this artificial solid electrolyte interface film and the manganese dioxide cathode is 150 to 400 mAh g. -1 .

11. The zinc-ion battery negative electrode regulated by the artificial solid electrolyte interface film as described in claim 10, characterized in that, The contact angle of the negative electrode in a zinc-ion battery regulated by an artificial solid electrolyte interface film is 20°. o ~ 60 o .

12. The application of the zinc-ion battery negative electrode regulated by the artificial solid electrolyte interface film as described in any one of claims 1-11 as a zinc-ion battery negative electrode.

13. The application as described in claim 12, characterized in that, The zinc-ion battery is an aqueous zinc-ion battery.

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