A method for inhibiting dendrite growth on a zinc foil surface
By forming a zinc-silane composite layer on the surface of zinc foil, the problem of dendrite growth in zinc-ion batteries was solved, thereby improving the electrochemical performance and cycle stability of zinc-ion batteries.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HEBEI UNIV OF TECH
- Filing Date
- 2023-12-14
- Publication Date
- 2026-06-02
Smart Images
Figure CN117802489B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of new energy materials and electrochemistry, and relates to an engineering treatment of the anode interface of zinc-ion batteries, and in particular to a zinc foil surface treatment method for inhibiting dendrite growth. Background Technology
[0002] Rechargeable aqueous zinc batteries with zinc metal anodes have high specific capacity (820 mAh / g and 5855 mAh / cm³). 3 Zinc anodes have attracted considerable attention as a promising solution for clean electrochemical energy storage due to their advantages, including a suitable reduction potential (-0.76V relative to the standard hydrogen electrode), inherent safety, low cost, environmental friendliness, and abundant zinc reserves. Despite these advantages, the practical application of zinc anodes is still hampered by dendrite growth and corrosive electrolytes. The non-uniform surface of commercial zinc metal, characterized by protrusions, promotes dendrite growth and uneven nucleation, ultimately leading to poor battery cycle stability, low reversibility, and reduced lifespan.
[0003] Currently, the industry uses wet chemical methods to prevent dendrite growth. Due to its simplicity and cost-effectiveness, wet chemical methods are widely used to generate thin films on zinc substrates to prevent dendrite growth. However, when using this method, the use of passivation layers during electroplating and stripping can lead to an increase in interface resistance and nucleation overpotential, which will ultimately reduce the rate performance of zinc-ion batteries and thus hinder their practical application.
[0004] Therefore, it is necessary to develop a zinc foil surface treatment method for zinc-ion batteries that can prevent dendrite formation without negatively affecting battery performance. Summary of the Invention
[0005] In view of this, in order to solve the above-mentioned technical problems, the present invention proposes a simple and short preparation cycle zinc foil surface treatment method to suppress dendrite growth. The zinc foil surface after treatment can generate a zinc-silane composite layer and zinc with (002) crystal orientation. The composite layer has a strong zinc ion adsorption capacity, which can improve ion dynamics, promote uniform zinc coating and peeling, and the preferred (002) crystal plane can induce parallel growth of zinc metal and resist electrolyte corrosion, thereby effectively suppressing zinc dendrites and stabilizing the electrode / electrolyte interface.
[0006] To achieve the above objectives, the technical solution of the present invention is implemented as follows:
[0007] This invention provides a zinc foil surface treatment method for inhibiting dendrite growth, comprising the following steps:
[0008] S1. The zinc foil after surface ultrasonic cleaning is immersed in an acidic mixture and acid etching is performed to obtain a zinc foil with a preferred zinc (002) crystal plane.
[0009] S2. Zinc foil with a preferred zinc (002) crystal plane is immersed in a mercaptosilane coupling agent solution. After hydrolysis, a zinc-silane composite layer with a nanostructure is formed on the surface of the zinc foil.
[0010] S3. After drying, zinc foil with a zinc-silane composite layer on the surface is obtained as zinc foil that can inhibit dendrite growth.
[0011] This invention employs a method where zinc foil is first thoroughly immersed in an acidic solution, and then etched with acid to obtain zinc foil with (002) crystal planes. This zinc foil with (002) crystal planes is then immersed in a mercaptosilane coupling agent solution, undergoing a hydrolysis reaction to form a nanostructured zinc-silane composite layer on the zinc foil surface. The zinc foil obtained using this specific acid-first-silane coupling agent treatment method exhibits excellent properties, resisting electrolyte corrosion, effectively inhibiting zinc dendrite formation, and stabilizing the electrode / electrolyte interface. If other treatment methods are used, such as immersing the zinc foil in a silane coupling agent solution first... The treatment method of immersing zinc foil in acid after coagulation involves reacting the zinc foil in a silane coupling agent to form a thin film before acid treatment. Since the zinc foil surface is already covered by the film, it is difficult to etch the 002 crystal plane, affecting the final performance. Another method is to immerse the zinc foil in a mixture of acid and silane coupling agent. Although the reaction rate between zinc foil and acid is faster than that between silane coupling agent, the zinc foil surface also reacts with the silane coupling agent, resulting in insufficient 002 crystal plane formation by acid etching on the zinc foil surface, which also affects the final performance.
[0012] In some preferred embodiments of the zinc foil surface treatment method for inhibiting dendrite growth of the present invention, in step S1, the temperature of the acidic mixture is controlled at 45-75°C, which has a good promoting effect on acid etching.
[0013] In some preferred embodiments of the zinc foil surface treatment method for inhibiting dendrite growth of the present invention, in step S1, the acidic mixture is prepared by dissolving acid in anhydrous ethanol and deionized water, wherein the volume ratio of anhydrous ethanol to deionized water is (18-25):1, and the concentration of acid is 0.01-0.2 mol / L.
[0014] Anhydrous ethanol can act as a dispersant; an appropriate amount of acid can better induce the parallel growth of Zn through the (002) interface generated after corroding the zinc foil surface, avoid the tip effect, and better inhibit the formation of dendrites.
[0015] In some preferred embodiments of the zinc foil surface treatment method for inhibiting dendrite growth of the present invention, the acid is acetic acid, phosphoric acid, boric acid, nitric acid, carbonic acid, or lactic acid.
[0016] In some preferred embodiments of the zinc foil surface treatment method for inhibiting dendrite growth of the present invention, in step S2, the mercaptosilane coupling agent solution is prepared by dissolving a silane coupling agent in anhydrous ethanol and deionized water, wherein the volume ratio of anhydrous ethanol, mercaptosilane coupling agent and deionized water is (18-25):(0.25-3):1.
[0017] An appropriate ratio of mercaptosilane to deionized water can lead to a strong interaction between Si-O-Zn and silane, resulting in a tighter and more durable interface between the zinc foil and the modified layer.
[0018] In some preferred embodiments of the zinc foil surface treatment method for inhibiting dendrite growth of the present invention, the mercaptosilane coupling agent is 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, or 3-mercaptopropyltriaminopropyltrimethoxysilane.
[0019] In some preferred embodiments of the zinc foil surface treatment method for inhibiting dendrite growth of the present invention, in step S1, the immersion time in the acidic mixture is 1 to 4 hours.
[0020] In some preferred embodiments of the zinc foil surface treatment method for inhibiting dendrite growth of the present invention, in step S2, the immersion time in the mercaptosilane coupling agent solution is 1 to 4 hours, which avoids insufficient dendrite inhibition effect due to short treatment time, and also avoids negative impact on battery performance due to excessive coating thickness caused by excessive treatment time.
[0021] In some preferred embodiments of the zinc foil surface treatment method for inhibiting dendrite growth of the present invention, in step S3, the drying temperature is 90-150°C and the heating time is 1-3 hours.
[0022] In another aspect, the present invention provides a zinc foil with dendrite growth suppressed after being treated by the aforementioned zinc foil surface treatment method.
[0023] Compared with existing technologies, the zinc foil surface treatment method for inhibiting dendrite growth described in this invention has the following advantages:
[0024] (1) The zinc foil surface treatment method for inhibiting dendrite growth described in this invention has a simple preparation process, a short preparation cycle, and is suitable for large-scale surface treatment of zinc foil.
[0025] (2) The zinc foil surface treatment method for inhibiting dendrite growth described in this invention utilizes the strong interaction between Si-O-Zn and silane to make the interface between the zinc foil and the modified layer more durable, and the nanostructured layer can increase the selective deposition of Zn. 2+The surface area is increased to improve electroactive activity and reduce the current density in the region that restricts dendrite growth; the preferred (002) crystal plane can induce parallel growth of Zn metal and resist corrosion by aqueous electrolytes, thereby effectively suppressing Zn dendrites and stabilizing the electrode / electrolyte interface.
[0026] (3) The zinc foil surface treatment method for inhibiting dendrite growth described in this invention adopts a treatment method of first soaking in acid and then soaking in mercaptosilane coupling agent. The zinc foil is first fully soaked in acidic solution, and zinc foil with 002 crystal facet is obtained under acid etching. The zinc foil with 002 crystal facet is then soaked in mercaptosilane coupling agent solution. After hydrolysis reaction, a zinc-silane composite layer with nanostructure is formed on the surface of the zinc foil, which can resist the corrosion of electrolyte, effectively inhibit zinc dendrites, and stabilize the electrode / electrolyte interface. Attached Figure Description
[0027] Figure 1 SEM images of unprocessed blank zinc foil and zinc foils obtained in Examples 1-3 are shown, where Image A is unprocessed blank zinc foil, Image B is zinc foil obtained in Example 2, Image C is zinc foil obtained in Example 1, and Image D is zinc foil obtained in Example 3.
[0028] Figure 2 XRD patterns of zinc foil obtained in Example 1, untreated blank zinc foil, and zinc foil obtained in Verification Examples 1-3;
[0029] Figure 3 SEM images of untreated blank zinc foil and zinc foil obtained in Example 1 after immersion in acidic electrolyte for one week, where Image A is the untreated blank zinc foil and Image B is the zinc foil obtained in Example 1;
[0030] Figure 4 The contact angles of untreated blank zinc foil, zinc foil obtained in Example 1, and zinc foil obtained in Comparative Example 1 in 2 mol / L ZnSO4 solution;
[0031] Figure 5 Coulombic efficiency performance tests were conducted on the untreated blank zinc foil, the zinc foil obtained in Comparative Example 1, the zinc foil obtained in Verification Example 1, and the zinc foil obtained in Example 1.
[0032] Figure 6 Cyclic performance tests were conducted on untreated blank zinc foil, zinc foil obtained in Comparative Example 1, zinc foil obtained in Verification Example 1, and zinc foil obtained in Example 1. Detailed Implementation
[0033] Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art. Unless otherwise specified, the experimental reagents used in the following embodiments are conventional biochemical reagents; and the experimental methods described are conventional methods.
[0034] The present invention will now be described in detail with reference to the embodiments and accompanying drawings.
[0035] Example 1
[0036] Step 1: Add 90ml of ethanol to a beaker, then add 4ml of deionized water and 500μl of acetic acid. Stir the solution in a 60℃ water bath for 2 hours to obtain a well-mixed acidic solution.
[0037] Step 2: Cut a piece of zinc foil and sonicate it in an alcohol solution for 10 minutes. Remove the zinc foil and wipe off any residual liquid on the surface. Soak the cleaned zinc foil in the prepared acidic mixture for 2 hours.
[0038] Step 3: Add 90ml of ethanol to a beaker, then add 4ml of deionized water and 6ml of 3-mercaptopropyltrimethoxysilane. Stir the solution at room temperature for 2 hours to obtain a well-mixed mercaptosilane coupling agent solution. Immerse the acid-treated zinc foil in the mercaptosilane coupling agent solution for 2 hours.
[0039] Step 4: Place the zinc foil soaked in the mercaptosilane coupling agent solution into a 100°C drying oven and heat for 2 hours to obtain zinc foil that can inhibit dendrite growth.
[0040] Example 2
[0041] Step 1: Add 90ml of ethanol to a beaker, then add 4ml of deionized water and 500μl of phosphoric acid. Stir the solution for 2 hours under a 60℃ water bath to obtain a well-mixed acidic solution.
[0042] Step 2: Cut a piece of zinc foil and sonicate it in an alcohol solution for 10 minutes. Remove the zinc foil and wipe off any residual liquid on the surface. Soak the cleaned zinc foil in the prepared acidic mixture for 2 hours.
[0043] Step 3: Add 90ml of ethanol to a beaker, then add 3ml of deionized water and 6ml of 3-mercaptopropylmethyldimethoxysilane. Stir the solution at room temperature for 2 hours to obtain a well-mixed mercaptosilane coupling agent solution. Immerse the acid-treated zinc foil in the mercaptosilane coupling agent solution for 1 hour.
[0044] Step 4: Place the zinc foil soaked in the mercaptosilane coupling agent solution into a 100°C drying oven and heat for 2 hours to obtain zinc foil that can inhibit dendrite growth.
[0045] Example 3
[0046] Step 1: Add 90ml of ethanol to a beaker, then add 4ml of deionized water and 500μl of phosphoric acid. Stir the solution for 2 hours under a 60℃ water bath to obtain a well-mixed acidic solution.
[0047] Step 2: Cut a piece of zinc foil and sonicate it in an alcohol solution for 10 minutes. Remove the zinc foil and wipe off any residual liquid on the surface. Soak the cleaned zinc foil in the prepared acidic mixture for 2 hours.
[0048] Step 3: Add 90ml of ethanol to a beaker, then add 6ml of deionized water and 6ml of 3-mercaptopropyltriaminopropyltrimethoxysilane. Stir the solution at room temperature for 2 hours to obtain a well-mixed mercaptosilane coupling agent solution. Immerse the acid-treated zinc foil in the mercaptosilane coupling agent solution for 4 hours.
[0049] Step 4: Place the zinc foil soaked in the mercaptosilane coupling agent solution into a 100°C drying oven and heat for 2 hours to obtain zinc foil that can inhibit dendrite growth.
[0050] Example 4
[0051] Step 1: Add 90ml of ethanol to a beaker, then add 4ml of deionized water and 500μl of lactic acid. Stir the solution for 2 hours under a 60℃ water bath to obtain a well-mixed acidic solution.
[0052] Step 2: Cut a piece of zinc foil and sonicate it in an alcohol solution for 10 minutes. Remove the zinc foil and wipe off any residual liquid on the surface. Soak the cleaned zinc foil in the prepared acidic mixture for 2 hours.
[0053] Step 3: Add 90ml of ethanol to a beaker, then add 2ml of deionized water and 6ml of 3-mercaptopropyltrimethoxysilane. Stir the solution at room temperature for 2 hours to obtain a well-mixed mercaptosilane coupling agent solution. Immerse the acid-treated zinc foil in the mercaptosilane coupling agent solution for 2 hours.
[0054] Step 4: Place the zinc foil soaked in the mercaptosilane coupling agent solution into a 100°C drying oven and heat for 2 hours to obtain zinc foil that can inhibit dendrite growth.
[0055] Verification Example 1
[0056] 1) Add 90 ml of ethanol to a beaker, then add 4 ml of deionized water and 500 μl of acetic acid. Stir the solution in a 60°C water bath for 2 hours to obtain a well-mixed acidic solution.
[0057] 2) Cut a piece of zinc foil and place it in an alcohol solution for ultrasonic treatment for 10 minutes. Remove the zinc foil and wipe off any residual liquid on the surface. Soak the cleaned zinc foil in the prepared acidic mixture for 2 hours.
[0058] 3) Place the acid-treated zinc foil in a 100℃ drying oven and heat for 2 hours to obtain the surface-treated zinc foil.
[0059] Verification Example 2
[0060] Based on Verification Example 1, the difference is that it was soaked in an acidic mixture for 1 hour.
[0061] Verification Example 3
[0062] Based on Verification Example 1, the difference is that it was soaked in an acidic mixture for 4 hours.
[0063] Comparative Example 1
[0064] 1) Add 90 ml of ethanol to a beaker, then add 4 ml of deionized water and 6 ml of 3-mercaptopropyltrimethoxysilane. Stir the solution at room temperature for 2 hours to obtain a well-mixed mercaptosilane coupling agent solution.
[0065] 2) Cut a piece of zinc foil and place it in an alcohol solution for ultrasonic treatment for 10 minutes. Remove the zinc foil and wipe off any residual liquid on the surface. Place the cleaned zinc foil in the prepared mercaptosilane coupling agent solution for 2 hours.
[0066] 3) The zinc foil soaked in mercaptosilane coupling agent solution was placed in a 100℃ drying oven and heated for 2 hours to obtain zinc foil after surface treatment.
[0067] Results and Characterization
[0068] 1. The zinc foils obtained in Examples 1-3 and the untreated blank zinc foil were characterized by microstructure using scanning electron microscopy, such as... Figure 1 As shown, A is an untreated blank zinc foil with many scratches on its surface; B, C, and D are zinc foils treated in Examples 1 to 3, which show a nanostructured surface. This may be caused by selective etching of different crystal planes. The uneven etched surface can facilitate the uniform distribution of the electric field and promote the uniform nucleation and electroplating of Zn metal electrodes; the SEM image of the zinc foil obtained in Example 4 is similar to that in Examples 1 to 3, also showing a nanostructured surface, which will not be described in detail here.
[0069] 2. The zinc foil obtained in Example 1, the untreated blank zinc foil, and the zinc foil obtained in Verification Examples 1-3 were characterized by XRD, as follows: Figure 2 As shown in the figure, the untreated blank zinc foil exhibits peaks at 36°, 38° and 43°, corresponding to the characteristic peaks of the (002), (100) and (101) planes of crystalline zinc. The zinc foils after acid etching in Verification Examples 1 to 3 and the zinc foil treated in Example 1 have higher relative intensities in (002)-(100) diffraction compared to the blank zinc foil, indicating that a selective etching reaction has occurred.
[0070] 3. Immerse the untreated blank zinc foil and the zinc foil obtained in Example 1 in an acidic electrolyte for one week; as follows: Figure 3 As shown, Figure A is the SEM surface of the untreated blank zinc foil after being soaked in acidic electrolyte for one week, and Figure B is the SEM surface of the treated zinc foil in Example 1 after being soaked in acidic electrolyte for one week. It can be seen that the untreated zinc foil in Figure A has many large patches, while the surface in Figure B is relatively clean with fewer byproducts; this indicates that the zinc-silane composite layer can protect the zinc anode from electrolyte corrosion and reduce side reactions.
[0071] 4. The untreated blank zinc foil, the zinc foil obtained in Example 1, and the zinc foil obtained in Comparative Example 1 were subjected to a contact angle experiment with a 2 mol / L ZnSO4 solution. Figure 4 As shown, the contact angle of the zinc foil obtained in Example 1 is smaller than that of the untreated zinc foil and Comparative Example 1, indicating that Example 1 has better hydrophilicity.
[0072] 5. The zinc foil obtained in Example 1, the untreated blank zinc foil, the zinc foil obtained in Verification Example 1, and the zinc foil obtained in Comparative Example 1 were assembled into Zn / / Cu batteries, and tested at a current density of 10 mA cm⁻¹. -2 Below, the deposition amount is 1 mAh cm⁻¹ –2 CE, by Figure 5 It can be seen that an average CE of 99.6% was achieved in 2000 cycles, and the battery assembled from zinc foil obtained in Example 1 exhibited good electrochemical performance.
[0073] 6. The zinc foil obtained in Example 1, the untreated blank zinc foil, the zinc foil obtained in Verification Example 1, and the zinc foil obtained in Comparative Example 1 were assembled into Zn / / Zn symmetric cells, and tested at 1 mA / cm. -2 Current density and 1mAhcm -2 Cyclic stability under capacity constraints, by Figure 6 It can be seen that the battery assembled from the zinc foil obtained in Example 1 maintained stability for 1000 hours without any significant overpotential increase. This stability exceeded that of the untreated blank zinc foil, the zinc foil obtained in Verification Example 1, and the zinc foil obtained in Comparative Example 1. This indicates that the combined effect of the (002) crystal plane and the surface coating effectively suppressed side reactions, extended cycle durability, and reduced voltage hysteresis.
[0074] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A method for surface treatment of zinc foil to inhibit dendrite growth, characterized in that, Includes the following steps: S1. The zinc foil after surface ultrasonic cleaning is immersed in an acidic mixture and acid etching is performed to obtain a zinc foil with a preferred zinc (002) crystal plane. S2. Zinc foil with a preferred zinc (002) crystal plane is immersed in a mercaptosilane coupling agent solution. After hydrolysis, a zinc-silane composite layer with a nanostructure is formed on the surface of the zinc foil. S3. After drying, zinc foil with a zinc-silane composite layer on the surface is obtained as zinc foil that can inhibit dendrite growth.
2. The zinc foil surface treatment method for inhibiting dendrite growth according to claim 1, characterized in that: In S1, the temperature of the acidic mixture is controlled between 45 and 75°C.
3. The zinc foil surface treatment method for inhibiting dendrite growth according to claim 1, characterized in that: In S1, the acidic mixture is prepared by dissolving acid in anhydrous ethanol and deionized water, wherein the volume ratio of anhydrous ethanol to deionized water is (18-25):1, and the concentration of acid is 0.01-0.2 mol / L.
4. The zinc foil surface treatment method for inhibiting dendrite growth according to claim 3, characterized in that: The acid is acetic acid, phosphoric acid, boric acid, nitric acid, carbonic acid, or lactic acid.
5. The zinc foil surface treatment method for inhibiting dendrite growth according to claim 1, characterized in that: In S2, the mercaptosilane coupling agent solution is prepared by dissolving the silane coupling agent in anhydrous ethanol and deionized water, wherein the volume ratio of anhydrous ethanol, mercaptosilane coupling agent and deionized water is (18-25):(0.25-3):
1.
6. The zinc foil surface treatment method for inhibiting dendrite growth according to claim 5, characterized in that: The mercaptosilane coupling agent is 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, or 3-mercaptopropyltriaminopropyltrimethoxysilane.
7. The zinc foil surface treatment method for inhibiting dendrite growth according to claim 1, characterized in that: In S1, the soaking time in the acidic mixture is 1 to 4 hours.
8. The zinc foil surface treatment method for inhibiting dendrite growth according to claim 1, characterized in that: In step S2, the soaking time in the mercaptosilane coupling agent solution is 1 to 4 hours.
9. The zinc foil surface treatment method for inhibiting dendrite growth according to claim 1, characterized in that: In step S3, the drying temperature is 90–150°C, and the heating time is 1–3 hours.
10. A zinc foil for inhibiting dendrite growth, characterized in that: The zinc foil that inhibits dendrite growth is obtained by treating the zinc foil surface treatment method for inhibiting dendrite growth as described in any one of claims 1 to 9.