A water-based zinc ion battery negative electrode with an interface protection layer and a preparation method thereof

Abstract

This invention relates to the field of battery materials technology, and particularly to an aqueous zinc-ion battery anode with an interface protective layer and its preparation method. The aqueous zinc-ion battery anode includes a zinc anode and an interface protective layer sprayed onto the surface of the zinc anode. The interface protective layer is composed of perfluorosulfonic acid resin and boehmite interface bridging, and the interface protective layer is dense and uniformly covers the zinc anode. The preparation method involves thoroughly mixing perfluorosulfonic acid resin, boehmite, deionized water, and isopropanol in a specific ratio to form a homogeneous slurry, and then ultrasonically spraying it onto the zinc anode. This invention utilizes ultrasonic spraying to form a protective interface on the surface of the zinc metal anode, preventing corrosion from the aqueous electrolyte during cycling. Furthermore, the boehmite molecules contain zinc-loving hydroxyl groups, which promote zinc nucleation and uniform deposition, thereby inhibiting dendrite growth in the zinc anode. The resulting battery anode can be used to manufacture zinc-ion batteries with high specific capacity, excellent rate performance, and long cycle stability.

Description

Technical Field

[0001] This invention relates to the field of battery materials technology, and in particular to an aqueous zinc-ion battery anode with an interface protective layer and its preparation method. Background Technology

[0002] Lithium-ion batteries are the most widely studied battery energy storage system due to their high energy density and excellent long-cycle stability. However, with the popularization of large-scale energy storage and electric vehicle technologies, the drawbacks of lithium metal resource shortages have become apparent. Furthermore, the high price of lithium metal, the toxicity and flammability of organic electrolytes, and the stringent production requirements further hinder the development of lithium-ion batteries. Therefore, there is an urgent need to develop new secondary battery energy systems. As a potential candidate for lithium-ion batteries, aqueous zinc-ion batteries have enormous application potential in the field of large-scale energy storage.

[0003] Rechargeable zinc-ion batteries have been at the forefront of battery research for the past few years. Zinc is abundant on Earth and non-toxic, offering a simple, low-cost, and highly safe battery energy system for the future. While aqueous zinc-ion batteries offer numerous advantages, their practical application is still hampered by issues at the interface of the aqueous electrolyte and the metal anode, such as dendrite growth, hydrogen evolution reaction, and corrosion or passivation. These problems lead to degraded battery performance, capacity decay, and shortened cycle life, hindering their practical application.

[0004] Several artificial solid electrolyte anode interface protective layers have been developed to address these issues. However, most of the reported interface layers exhibit poor adhesion between particles or to the zinc anode, making them prone to cracking during cycling and unable to achieve proper Zn protection. 2+ Effective regulation of ion migration pathways and migration kinetics is crucial; on the other hand, interface protective layers generally involve complex preparation processes and high production costs, and the products have poor physicochemical stability, making it difficult for them to remain stable in salt electrolytes for a long time. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing technologies and propose an aqueous zinc-ion battery anode with an interface protective layer and its preparation method, which can promote zinc nucleation and uniform deposition and inhibit dendrite growth of zinc anode.

[0006] To achieve the above objectives, the present invention adopts the following specific technical solution:

[0007] The present invention provides a method for preparing an aqueous zinc-ion battery negative electrode with an interface protective layer, comprising the following steps:

[0008] S1. Boehmite is placed in deionized water and stirred to mix. After centrifugation to separate the solid, it is dried to obtain boehmite powder.

[0009] S2. Weigh the perfluorosulfonic acid resin solution and boehmite powder and place them in a container. Add the organic dispersion and deionized water, stir, and sonicate to obtain a slurry.

[0010] S3. An aqueous zinc-ion battery anode with a perfluorosulfonic acid resin / boehmite interface protective layer is prepared by ultrasonic spraying of slurry onto the zinc anode.

[0011] Furthermore, the organic dispersion is selected from at least one of n-propanol and isopropanol, the mass ratio of perfluorosulfonic acid resin to boehmite powder is 1:0.3 to 1:0.7, preferably 1:0.6; the volume ratio of organic dispersion to deionized water is 1:1 to 1:2, preferably 1:1.5.

[0012] Furthermore, in step S2, the stirring time is 20-30 min, and the sonication time is 10-20 min.

[0013] Further, in step S3, the slurry is sprayed onto the zinc anode using an ultrasonic sprayer at a speed of 200–300 μL / min for 2–3 hours.

[0014] The aqueous zinc-ion battery anode with an interface protective layer provided by the present invention is prepared by the above-described method and includes a zinc anode and an interface protective layer sprayed on the surface of the zinc anode. The interface protective layer is composed of perfluorosulfonic acid resin and boehmite.

[0015] Furthermore, the interface protective layer is ultrasonically sprayed onto the surface of the zinc anode, with a thickness of 6–8 μm and a dense and uniform film morphology.

[0016] The present invention can achieve the following technical effects:

[0017] This invention utilizes ultrasonic spraying to form a dense and uniform protective interface on the surface of a zinc metal anode, preventing corrosion from aqueous electrolytes during cycling. Furthermore, the boehmite molecules contain zinc-loving hydroxyl groups, which promote zinc nucleation and uniform deposition, thereby inhibiting dendrite growth in the zinc anode. The aqueous zinc-ion battery anode with an interface protective layer prepared by this invention can be used to fabricate zinc-ion batteries with high specific capacity, excellent rate performance, and long cycle stability. Moreover, the preparation method is low-cost, high-performance, simple, and reproducible, showing broad prospects for industrial application. Attached Figure Description

[0018] Figure 1 This is the X-ray diffraction pattern of the negative electrode of an aqueous zinc-ion battery with an interface protective layer prepared according to Example 1 of the present invention.

[0019] Figure 2This is a scanning electron microscope image of the aqueous zinc-ion battery negative electrode with an interface protective layer prepared according to Example 1 of the present invention.

[0020] Figure 3 This is a cycle performance diagram of a zinc-ion battery assembled with an interface protective layer using an aqueous zinc-ion battery negative electrode prepared according to Embodiment 1 of the present invention.

[0021] Figure 4 This is a rate performance diagram of a zinc-ion battery assembled with an interface protective layer using an aqueous zinc-ion battery negative electrode prepared according to Embodiment 1 of the present invention. Detailed Implementation

[0022] In the following description, embodiments of the invention will be described with reference to the accompanying drawings. In the description below, the same modules are denoted by the same reference numerals. Where the same reference numerals are used, their names and functions are also the same. Therefore, their detailed description will not be repeated.

[0023] 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 specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not constitute a limitation thereof.

[0024] This invention provides a method for preparing an aqueous zinc-ion battery negative electrode with an interface protective layer, comprising the following steps:

[0025] S1. Boehmite is placed in deionized water and stirred to mix. After centrifugation to separate the solid, it is vacuum dried to obtain boehmite powder.

[0026] S2. Weigh perfluorosulfonic acid resin and boehmite powder and place them in a container. Add organic dispersion and deionized water, stir, and sonicate to obtain a slurry.

[0027] The organic dispersion is selected from at least one of n-propanol and isopropanol. The mass ratio of perfluorosulfonic acid resin to boehmite powder is 1:0.3 to 1:0.7, preferably 1:0.6. The volume ratio of organic dispersion to deionized water is 1:1 to 1:2, preferably 1:1.5. The stirring time is 20 to 30 min, and the ultrasonic treatment is performed for 10 to 20 min.

[0028] S3. An aqueous zinc-ion battery anode with a perfluorosulfonic acid resin / boehmite interface protective layer is prepared by ultrasonic spraying of slurry onto the zinc anode.

[0029] The slurry was drawn into a 50mL special spraying syringe and installed on an ultrasonic sprayer. The zinc anode was cleaned with alcohol, vacuum dried for 2 hours, and then placed on the substrate of the sprayer. The temperature was raised to 80℃, and the slurry was sprayed at a speed of 200-300μL / min for 2-3 hours. After the spraying was completed, the zinc anode was removed, and an aqueous zinc-ion battery anode with a perfluorosulfonic acid resin / boehmite interface protective layer was obtained.

[0030] The aqueous zinc-ion battery anode with a perfluorosulfonic acid resin / boehmite interface protective layer provided in this embodiment of the invention is prepared by the above-described method. It includes a zinc anode and an interface protective layer sprayed onto the surface of the zinc anode. The interface protective layer is composed of perfluorosulfonic acid resin and boehmite interface bridging. The interface protective layer is ultrasonically sprayed onto the surface of the zinc anode, and has a thickness of 6–8 μm, exhibiting a dense and uniform film morphology.

[0031] The zinc-ion battery performance testing method for the perfluorosulfonic acid resin / boehmite negative electrode interface protective layer prepared in this invention is as follows: A pre-coated zinc sheet is cut into pieces to serve as the negative electrode. NVO active material, polyvinylidene fluoride binder, and conductive Ketjen black are weighed and thoroughly ground. An appropriate amount of NMP is added and mixed to form a uniform black paste, which is then coated onto a current collector to form the positive electrode. The electrolyte system is 2M ZnSO4. A button cell is assembled using a glass fiber separator, etc. The charge / discharge current density used for testing cycle performance is 500 mA·g. -1 .

[0032] This invention utilizes ultrasonic spraying to form a dense and uniform protective interface on the surface of a zinc metal anode, preventing corrosion from aqueous electrolytes during cycling. Furthermore, the boehmite molecules contain zinc-loving hydroxyl groups, which can promote zinc nucleation and uniform deposition, thereby inhibiting dendrite growth in the zinc anode. The zinc anode protected by this interface layer exhibits high stability, high rate performance, and long cycle life.

[0033] This invention also provides a method for preparing the above-mentioned perfluorosulfonic acid resin / boehmite anode interface protective layer on a large area, which is low-cost, high-performance, simple in process, and has good repeatability. The composite film is composed of perfluorosulfonic acid resin / boehmite on a zinc anode, and the interface layer has a dense and uniform film morphology. Compared with the ordinary blade coating method, the ultrasonic spraying method used in this invention has the advantages of controllable thickness, uniform spraying, good repeatability, and large-area preparation.

[0034] In this invention, the perfluorosulfonic acid resin exhibits high adhesion, increasing the bonding between boehmite particles and the bonding between boehmite and the zinc anode. This enhances interfacial layer stability and zinc affinity, preventing corrosion and cracking of the zinc metal anode by the aqueous electrolyte during cycling and contributing to improved long-cycle stability of the battery. Boehmite possesses relatively high porosity and specific surface area, providing stable migration channels for zinc ions, allowing for rapid passage and increasing zinc ion migration kinetics. Furthermore, the presence of zinc-affinity hydroxyl groups in the boehmite molecule increases zinc affinity, inducing zinc ion nucleation and uniform deposition, thus helping to suppress dendrite growth in the zinc anode and improving battery stability, rate performance, and cycle life.

[0035] The following will describe the aqueous zinc-ion battery anode with an interface protective layer and its preparation method provided by the present invention with reference to specific embodiments.

[0036] Example 1

[0037] A portion of untreated boehmite was dissolved in deionized water and stirred continuously for 2 hours under magnetic stirring. The mixture was then transferred to a centrifuge tube and centrifuged. After centrifugation, the boehmite was vacuum dried at 60°C for 6 hours.

[0038] Weigh 0.27 g of boehmite powder and 3.2 mL of perfluorosulfonic acid resin solution into a beaker. Add 18 mL of deionized water and 12 mL of isopropanol to the beaker. Stir continuously for 30 min under magnetic stirring, then sonicate for 20 min to obtain a uniformly mixed milky white slurry. Use a 50 mL special ultrasonic spraying syringe to draw up the slurry and install it on an ultrasonic spraying instrument. Clean the zinc metal anode with alcohol, vacuum dry for 2 h, and then place it on the substrate of the spraying instrument. Heat to 80 °C. Set the program to spray the slurry at a spraying speed of 200–300 μL / min for 2–3 h. After spraying, a zinc anode with perfluorosulfonic acid resin / boehmite interface protection is obtained.

[0039] The coated zinc anode was labeled Nafion / BM@Zn, and the physicochemical properties of the sample were analyzed. The Nafion / BM@Zn anode prepared in this embodiment was assembled with a cathode to form a coin cell zinc-ion battery. Its material characterization and electrochemical performance are as follows: Figures 1-4 As shown:

[0040] Figure 1 This is the X-ray diffraction pattern of the aqueous zinc-ion battery negative electrode with an interface protective layer prepared in this embodiment. Figure 1 It can be seen that the presence of three boehmite diffraction characteristic peaks at 14.4°, 28.1° and 38.3° on the zinc anode indicates that the interface layer is fixed on the zinc surface.

[0041] Figure 2This is a scanning electron microscope (SEM) image of the aqueous zinc-ion battery negative electrode with an interface protective layer prepared in this embodiment. Figure 2 It can be seen that the thin film formed by the perfluorosulfonic acid resin and boehmite uniformly covers the surface of the zinc anode.

[0042] Figure 3 This is a cycle performance diagram of a zinc-ion battery assembled with an aqueous zinc-ion battery negative electrode having an interface protective layer, prepared in this embodiment. Figure 3 It can be seen that at 500mA·g -1 The discharge specific capacity remains at 271.7 mAh·g after 100 cycles at the current density. -1 It exhibits good long-term cycling stability.

[0043] Figure 4 This is a rate performance diagram of a zinc-ion battery assembled with an aqueous zinc-ion battery negative electrode having an interface protective layer, prepared in this embodiment. Figure 4 It can be seen that this anode material has excellent rate performance at 5000 mA·g. -1 It can still maintain 227.6 mAh·g under high current discharge conditions. -1 The discharge specific capacity when the current density returns to 200 mA·g -1 Afterwards, the discharge specific capacity can reach 317.8 mAh·g again. -1 .

[0044] Example 2

[0045] A portion of untreated boehmite was dissolved in deionized water and stirred continuously for 2 hours under magnetic stirring. The mixture was then transferred to a centrifuge tube and centrifuged. After centrifugation, the boehmite was vacuum dried at 60°C for 6 hours.

[0046] Weigh 0.27 g of boehmite powder and 1.6 mL of perfluorosulfonic acid resin solution into a beaker. Add 18 mL of deionized water and 12 mL of isopropanol to the beaker, and stir continuously for 30 min under magnetic stirring, followed by sonication for 20 min to obtain a uniformly mixed milky white slurry. Use a 50 mL special ultrasonic spraying syringe to draw up the slurry and install it on an ultrasonic spraying instrument. Clean the zinc metal anode with alcohol, vacuum dry for 2 h, and then place it on the substrate of the spraying instrument, heating it to 80°C. Set the program to spray the slurry for 2–3 h. After spraying, a zinc anode with perfluorosulfonic acid resin / boehmite interface protection is obtained.

[0047] Subsequently, the coated zinc anode was subjected to physicochemical property testing and analysis. The anode and cathode prepared in this embodiment were assembled into a coin cell zinc-ion battery, which was tested at 500 mA·g. -1 The discharge specific capacity can be maintained at 257.2 mAh·g after 100 cycles at the current density.-1 .

[0048] Example 3

[0049] A portion of untreated boehmite was dissolved in deionized water and stirred continuously for 2 hours under magnetic stirring. The mixture was then transferred to a centrifuge tube and centrifuged. After centrifugation, the boehmite was vacuum dried at 60°C for 6 hours.

[0050] Weigh 0.27 g of boehmite powder and 2.7 mL of perfluorosulfonic acid resin solution into a beaker. Add 18 mL of deionized water and 12 mL of isopropanol to the beaker, and stir continuously for 30 min under magnetic stirring, followed by sonication for 20 min to obtain a uniformly mixed milky white slurry. Use a 50 mL special ultrasonic spraying syringe to draw up the slurry and install it on an ultrasonic spraying instrument. Clean the zinc metal anode with alcohol, vacuum dry for 2 h, and then place it on the substrate of the spraying instrument, heating it to 80°C. Set the program to spray the slurry for 2–3 h. After spraying, a zinc anode with perfluorosulfonic acid resin / boehmite interface protection is obtained.

[0051] Subsequently, the coated zinc anode was subjected to physicochemical property testing and analysis. The anode and cathode prepared in this embodiment were assembled into a coin cell zinc-ion battery, which was tested at 500 mA·g. -1 At the specified current density, the discharge specific capacity remains at 255.4 mAh·g after 100 cycles. -1 .

[0052] Example 4

[0053] A portion of untreated boehmite was dissolved in deionized water and stirred continuously for 2 hours under magnetic stirring. The mixture was then transferred to a centrifuge tube and centrifuged. After centrifugation, the boehmite was vacuum dried at 60°C for 6 hours.

[0054] Weigh 0.27 g of boehmite powder and 3.7 mL of perfluorosulfonic acid resin solution into a beaker. Next, add 18 mL of deionized water and 12 mL of isopropanol to the beaker, and stir continuously for 30 min under magnetic stirring, followed by ultrasonication for 20 min to obtain a uniformly mixed milky white slurry. Use a 50 mL dedicated ultrasonic spraying syringe to draw up the slurry and install it onto an ultrasonic spraying instrument. Clean the zinc metal anode with alcohol, vacuum dry for 2 h, and then place it on the substrate of the spraying instrument, heating it to 80°C. Set the optimal program for slurry spraying, with a spraying time of 2–3 h. After spraying, a zinc anode with perfluorosulfonic acid resin / boehmite interface protection is obtained.

[0055] Subsequently, the coated zinc anode was subjected to physicochemical property testing and analysis. The anode and cathode prepared in this embodiment were assembled into a coin cell zinc-ion battery, which was tested at 500 mA·g. -1The discharge specific capacity can be maintained at 262.4 mAh·g after 100 cycles at the current density. -1 .

[0056] Example 5

[0057] A portion of untreated boehmite was dissolved in deionized water and stirred continuously for 2 hours under magnetic stirring. The mixture was then transferred to a centrifuge tube and centrifuged. After centrifugation, the boehmite was vacuum dried at 60°C for 6 hours.

[0058] Weigh 0.20 g of boehmite powder and 3.2 mL of perfluorosulfonic acid resin solution into a beaker. Next, add 18 mL of deionized water and 12 mL of isopropanol to the beaker, and stir continuously for 30 min under magnetic stirring, followed by ultrasonication for 20 min to obtain a uniformly mixed milky white slurry. Use a 50 mL ultrasonic spraying syringe to draw up the slurry and install it onto an ultrasonic spraying instrument. Clean the zinc metal anode with alcohol, vacuum dry for 2 h, and then place it on the substrate of the spraying instrument, heating it to 80°C. Set the optimal program for slurry spraying, with a spraying time of 2–3 h. After spraying, a zinc anode with perfluorosulfonic acid resin / boehmite interface protection is obtained.

[0059] Subsequently, the coated zinc anode was subjected to physicochemical property testing and analysis. The anode and cathode prepared in this embodiment were assembled into a coin cell zinc-ion battery, which was tested at 500 mA·g. -1 The discharge specific capacity can be maintained at 244.3 mAh·g after 100 cycles at the current density. -1 .

[0060] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0061] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

[0062] The specific embodiments of the present invention described above do not constitute a limitation on the scope of protection of the present invention. Any other corresponding changes and modifications made in accordance with the technical concept of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing an aqueous zinc-ion battery negative electrode with an interface protective layer, characterized in that, Includes the following steps: S1. Boehmite is placed in deionized water and stirred to mix. After centrifugation to separate the solid, it is dried to obtain boehmite powder. S2. Weigh the perfluorosulfonic acid resin solution and the boehmite powder and place them in a container. Add organic dispersion and deionized water, stir, and sonicate to obtain a slurry. S3. The slurry is sprayed onto the zinc anode by ultrasonic spraying to obtain an aqueous zinc-ion battery anode with a perfluorosulfonic acid resin / boehmite interface protective layer.

2. The method for preparing the aqueous zinc-ion battery negative electrode with an interface protective layer according to claim 1, characterized in that, The organic dispersion is selected from at least one of n-propanol and isopropanol, and the mass ratio of perfluorosulfonic acid resin to boehmite powder is 1:0.3 to 1:0.7; the volume ratio of the organic dispersion to deionized water is 1:1 to 1:

2.

3. The method for preparing the aqueous zinc-ion battery negative electrode with an interface protective layer according to claim 1, characterized in that, In step S2, the stirring time is 20-30 minutes, and the sonication time is 10-20 minutes.

4. The method for preparing the aqueous zinc-ion battery negative electrode with an interface protective layer according to claim 1, characterized in that, In step S3, the slurry is sprayed onto the zinc anode using an ultrasonic sprayer at a speed of 200-300 μL / min for 2-3 hours.

5. An aqueous zinc-ion battery negative electrode with an interface protective layer prepared by the preparation method according to any one of claims 1 to 4, characterized in that, It includes a zinc anode and an interface protective layer sprayed on the surface of the zinc anode, the interface protective layer being composed of perfluorosulfonic acid resin and boehmite.

6. The aqueous zinc-ion battery negative electrode with an interface protective layer according to claim 5, characterized in that, The interface protective layer is ultrasonically sprayed onto the surface of the zinc anode. The thickness of the interface protective layer is 6-8 μm, and the interface protective layer has a dense and uniform film morphology.

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