A method for preparing a zeolitic imidazolate framework / silicon air battery and an air battery
By preparing a zeolite imidazole ester framework ZIF-8 coating on the silicon anode surface of a silicon-air battery, the problems of silicon anode passivation and corrosion reaction were solved, extending battery life and improving battery performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- KUNMING UNIVERSITY
- Filing Date
- 2023-02-10
- Publication Date
- 2026-06-12
AI Technical Summary
During the discharge process, passivation and corrosion of the silicon anode surface in silicon-air batteries can hinder electrode reactions, affecting battery life and performance.
A ZIF-8/silicon composite electrode was prepared by coating the silicon anode surface with zeolite imidazole ester framework material ZIF-8 and using a solution growth method. This reduced the direct contact between the silicon substrate and water and the silicon dioxide passivation layer, thus inhibiting corrosion and passivation reactions.
It extends the lifespan of silicon-air batteries and improves their overall performance. By controlling the crystallinity and content of ZIF-8, it enhances the protective effect of the silicon anode.
Smart Images
Figure CN116247225B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of silicon-air battery technology, and in particular to a method for preparing a zeolite imidazole ester framework / silicon-air battery and an air battery thereof. Background Technology
[0002] In recent years, with the development of new energy storage and conversion technologies, various types of air batteries have emerged, most of which are metal-air batteries. Compared with metal-air batteries, silicon-air batteries have higher safety. On this basis, silicon-air batteries also have advantages such as lower cost and higher theoretical capacity and operating voltage (Materials 2019, 12(13):2134), so silicon-air batteries will also be an important option for solving energy problems.
[0003] During discharge, the silicon anode surface of a silicon-air battery undergoes passivation, silicate formation, and corrosion reactions under alkaline conditions.
[0004] Passivation reaction: Si(OH)4 → SiO2(s) + 2H2O
[0005] Silicate formation:
[0006] Corrosion reaction:
[0007] A portion of the Si(OH)4 generated by the anodic reaction gradually transforms into SiO2 and eventually deposits on the electrode surface, hindering further reaction between the electrode and the electrolyte—a phenomenon known as passivation. Simultaneously, self-corrosion of silicon occurs during the anodic reaction, generating hydrogen gas. Passivation and corrosion significantly impede the further development of silicon-air batteries (Journal of Industrial and Engineering Chemistry 112(2022)271–278). Therefore, coating the silicon anode surface to protect it holds promise for extending battery life and improving battery performance.
[0008] Zeolitic imidazolate frameworks (ZIFs) are a class of porous materials formed by the coordination of metal ions and organic ligands. Their inherent porosity, numerous functionalities, and exceptional thermal and chemical stability have led to their widespread application in various fields. For example, they are used in gas separation, adsorption, and storage; and as catalysts and catalyst supports in various catalytic reactions. ZIF-8 material exhibits excellent corrosion resistance and porous properties, hindering direct contact between water molecules, the silica passivation layer, and the silicon anode. Coating the silicon anode surface with ZIF-8 material may further improve the overall performance of silicon-air batteries. Summary of the Invention
[0009] The purpose of this invention is to provide a method for preparing a zeolite imidazole ester framework / silicon-air battery and an air battery. By using the zeolite imidazole ester framework material, the direct contact between the silicon substrate and water and the silicon dioxide passivation layer is reduced, and the occurrence of corrosion and passivation reactions is inhibited, thereby extending the life of the silicon-air battery.
[0010] According to one objective of the present invention, a method for preparing a zeolite imidazole ester framework / silicon-air battery is provided, comprising the following steps:
[0011] 1) After cleaning the silicon substrate, place the silicon wafer on a heating plate and heat and keep it warm;
[0012] 2) Add zinc acetate dropwise onto the silicon wafer substrate obtained in step 1), and heat until the solution evaporates to dryness;
[0013] 3) Place the dried silicon wafers in a box furnace for annealing;
[0014] 4) The silicon wafer substrate with zinc oxide grown in step 3) is calcined in a box furnace;
[0015] 5) Add 2-methylimidazole and DMF / H2O mixed solvent sequentially to the reaction vessel and sonicate.
[0016] 6) Place the silicon wafer substrate on which zinc oxide has been grown in step 4) and the mixed solution obtained in step 5) into a hydrothermal reactor and seal it tightly.
[0017] 7) After sealing the reaction vessel from step 6), place it in an oven to carry out a solvothermal reaction;
[0018] 8) After the silicon wafer has cooled naturally, use tweezers to remove the reacted substrate and wash it several times with ethanol.
[0019] 9) Add platinum carbon to the mixed solution of naphthol and isopropanol, and sonicate until fully mixed;
[0020] 10) Coat the mixture obtained in step 9) onto the surface of carbon paper and allow the solution to evaporate to dryness.
[0021] 11) Prepare a potassium hydroxide solution as the electrolyte for a silicon-based air battery;
[0022] 12) After loading the zeolite imidazole ester skeleton / silicon composite material obtained in step 8) and the carbon paper obtained in step 10) into the existing air battery mold, add the electrolyte obtained in step 11), let it stand for 2 hours, and then test the battery discharge.
[0023] Further, in step 1), the silicon wafer has a diameter of 10mm to 80mm and a thickness of 200μm to 800μm, and the heating plate heats it to 70℃ to 120℃ and keeps it warm.
[0024] Further, in step 2), 5 mL to 10 mL of 0.1 mmol / L to 1 mmol / L zinc acetate is added dropwise three times to the silicon wafer substrate obtained in step 1), and the solution is heated until it evaporates to dryness.
[0025] Further, in step 3), the dried silicon wafer is placed in a box furnace and annealed at 300℃~350℃ for 30min~40min to convert zinc acetate seed crystals into zinc oxide crystals; in step 4), the silicon wafer substrate with zinc oxide grown in step 3) is placed in a box furnace again and calcined at 450℃~500℃ for 30min~40min to remove the surfactants adsorbed on the surface.
[0026] Further, in step 5), 0.5 mM to 20 mM of 2-methylimidazole and 16 mL to 32 mL of DMF / H2O mixed solvent are added to the reaction vessel in sequence. The DMF / H2O is mixed in a ratio of 2:1 to 5:1. The reaction vessel containing the mixed solution is ultrasonically treated for 5 min to 10 min.
[0027] Further, in step 6), the silicon wafer substrate on which zinc oxide has been grown in step 4) is placed upside down in a reactor of appropriate size, and the zeolite imidazole ester framework crystals are grown downwards.
[0028] Further, in step 7), the reaction vessel is covered and placed in an oven at 70℃~100℃ for solvothermal reaction for 24h~48h; in step 9), 2.8mg~5.6mg of platinum carbon is added to a mixed solution of 700μL~1000μL naphthol and 300μL~500μL isopropanol, and ultrasonically treated for 1h~1.5h until the mixture gradually becomes viscous.
[0029] Furthermore, in step 10), the carbon paper is selected from a three-layer structure consisting of a nickel mesh, a waterproof layer, and carbon paper; in step 11), the electrolyte for the silicon-based air battery is a 1-10 mol / L potassium hydroxide solution.
[0030] According to another objective of the present invention, the present invention provides a zeolite imidazole ester framework / silicon-air battery, which is prepared by the above method.
[0031] Furthermore, the present invention provides a zeolite imidazole ester framework / zinc-air battery or a zeolite imidazole ester framework / germanium-air battery, wherein the silicon wafer substrate is replaced with a zinc wafer substrate or a germanium wafer substrate, and the battery is prepared by the above method.
[0032] Beneficial effects
[0033] This invention employs a solution growth method to prepare a zinc oxide crystal structure on a silicon substrate, and then prepares a ZIF-8 / silicon composite electrode through a solvothermal reaction using a DMF / H2O mixture. The ZIF-8 / silicon composite silicon anode material is assembled with a platinum-carbon cathode and KOH solution in an air battery mold to construct a ZIF-8 / silicon air battery. During the discharge process of this silicon-based air battery, the ZIF-8 helps reduce the direct contact between the silicon substrate and water and the silicon dioxide passivation layer, inhibiting corrosion and passivation reactions, thereby extending the lifespan of the silicon air battery. Attached Figure Description
[0034] Figure 1 This is a comparison chart showing the hydrophilicity angle measurements of a blank silicon wafer and a ZIF-8 / silicon composite electrode in an embodiment of the present invention.
[0035] Figure 2 This is a flowchart illustrating the preparation of a zeolite imidazole ester framework ZIF-8 / silicon composite electrode according to an embodiment of the present invention.
[0036] Figure 3 A scanning electron microscope (SEM) planar image of the ZIF-8 / silicon composite electrode obtained in Example 1 of the present invention;
[0037] Figure 4 This is a scanning electron microscope (SEM) planar image of the ZIF-8 / silicon composite electrode obtained in Example 2 of the present invention;
[0038] Figure 5 The XRD patterns are those of 0.5 mM zinc acetate titrated with 10 mM, 15 mM and 20 mM 2-methylimidazole after conversion.
[0039] Figure 6 The XRD patterns are those of 0.1 mM zinc acetate titrated with 10 mM, 15 mM and 20 mM 2-methylimidazole after conversion.
[0040] Figure 7 The discharge curves of the ZIF-8 / silicon composite electrodes prepared under three different 2-methylimidazole contents in Example 1 of this invention are compared with those of a blank silicon wafer.
[0041] Figure 8 The discharge curves of the ZIF-8 / silicon composite electrode prepared under three different 2-methylimidazole contents in Example 2 of this invention are compared with those of a blank silicon wafer. Detailed Implementation
[0042] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0043] In the description of this invention, it should be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," and "counterclockwise," etc., indicating orientation or positional relationships, are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this invention.
[0044] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the stated features. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly specified. Furthermore, the terms "installed," "connected," and "linked" should be interpreted broadly; for example, they may refer to a fixed connection, a detachable connection, or an integral connection; they may refer to a mechanical connection or an electrical connection; they may refer to a direct connection or an indirect connection through an intermediate medium; and they may refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.
[0045] Example 1
[0046] like Figure 2 As shown, a method for preparing a zeolite imidazole ester framework / silicon-air battery includes the following steps:
[0047] 1) After cleaning the silicon substrate, place the silicon wafer on a heating plate and heat it to 70℃~120℃ and keep it warm;
[0048] 2) Add 5 mL to 10 mL of zinc acetate with a concentration of 0.1 mmol / L to 1 mmol / L to the silicon wafer substrate obtained in step 1), and heat until the solution evaporates to dryness;
[0049] 3) Place the dried silicon wafers in a box furnace and anneal them at 300℃~350℃ for 30min~40min. This will convert zinc acetate to zinc oxide.
[0050] 4) The silicon wafer substrate with zinc oxide grown in step 3) is calcined in a box furnace at 450℃~500℃ for 30min~40min to remove the surfactant adsorbed on the surface.
[0051] 5) Add 0.5mM to 20mM 2-methylimidazole and DMF / H2O mixed solvent in a ratio of 2:1 to 5:1 to a reaction vessel of appropriate size, and sonicate for 5 min to 10 min respectively;
[0052] 6) Place the silicon wafer substrate on which zinc oxide has been grown in step 4) and the mixed solution obtained in step 5) into a hydrothermal reactor and seal it tightly.
[0053] 7) After sealing the reaction vessel from step 6), place it in an oven and react at 70℃~100℃ for 24h~48h;
[0054] 8) After the silicon wafer has cooled naturally, use tweezers to remove the reacted substrate and wash it several times with ethanol.
[0055] 9) Add platinum carbon to a mixed solution of naphthol and isopropanol, and sonicate until fully mixed;
[0056] 10) Coat the mixture obtained in step 9) onto the surface of carbon paper and allow the solution to evaporate to dryness.
[0057] 11) Prepare a 6 mol / L potassium hydroxide solution as the electrolyte for the air battery.
[0058] 12) After loading the ZIF-8 / silicon composite material obtained in step 8) and the carbon paper obtained in step 10) into the existing air battery mold, add the electrolyte obtained in step 11), let it stand for 1 hour, and then test the battery discharge.
[0059] Example 2
[0060] like Figure 2 As shown, first, a standard cleaned silicon wafer (size: 40mm) is placed on a hot plate and heated to 100℃ after cleaning the silicon substrate. Then, 9.8ml of 0.5mmol / L zinc acetate is added dropwise to the silicon substrate and heated until the solution evaporates to dryness. The evaporated silicon wafer is then placed in a box furnace and annealed at 350℃ for 30min. This process converts zinc acetate to zinc oxide.
[0061] The resulting silicon wafer substrate with grown zinc oxide was then calcined in a box furnace at 500°C for 30 minutes to remove the surfactants adsorbed on the surface.
[0062] 10 mM, 15 mM, and 20 mM 2-methylimidazole and DMF / H2O (16 mL 3:1) mixed solvent were sequentially added to a 100 mL reaction vessel and sonicated for 5 min. The silicon wafer substrate with grown zinc oxide and the solutions of 10 mM, 15 mM, and 20 mM 2-methylimidazole and DMF / H2O mixed solvent were placed in a hydrothermal reaction vessel and sealed tightly. The sealed reaction vessel was placed in an oven and reacted at 90 °C for 24 h. After natural cooling, the reacted silicon wafer substrate was removed with tweezers and washed several times with ethanol.
[0063] Add 2.8 mg of platinum carbon to a mixed solution of 700 μL of naphthol and 300 μL of isopropanol, sonicate for 1.5 h, and mix thoroughly; coat the obtained mixture onto the surface of carbon paper and allow the solution to evaporate to dryness.
[0064] A 6 mol / L potassium hydroxide solution was prepared as the electrolyte for the air battery. The obtained ZIF-8 / silicon composite material and the obtained carbon paper were placed into an existing air battery mold, and then the prepared potassium hydroxide electrolyte was added. After standing for 2 hours, the battery discharge performance was tested.
[0065] like Figure 3 The image shown is a scanning electron microscope (SEM) planar view of the ZIF-8 / silicon composite electrode obtained in this embodiment. Figure 3 Figure (a) shows the morphology of the product after titration with 0.5 mM zinc acetate and conversion with 10 mM 2-methylimidazole; Figure 3 Figure (b) shows the morphology of the solution after titration with 0.5 mM zinc acetate and conversion with 15 mM 2-methylimidazole; Figure 3 Figure (c) shows the morphology of the product after titration with 0.5 mM zinc acetate followed by conversion with 20 mM 2-methylimidazole.
[0066] like Figure 7 As shown, the discharge time of the air battery obtained in this embodiment is longer than that of the blank silicon wafer, with the 10mM dimethylimidazole reaching a maximum of 412h.
[0067] like Figure 1 As shown, Figure 1 (a) shows the hydrophilicity angle measurement of a blank silicon wafer; Figure 1 (b) shows the hydrophilicity angle measurement of the ZIF-8 / silicon composite electrode.
[0068] like Figure 5The image shows the XRD patterns of the product after titration with 0.5 mM zinc acetate and subsequent conversion with 10 mM, 15 mM, and 20 mM 2-methylimidazole in this embodiment.
[0069] Example 3
[0070] like Figure 2 As shown, first, after cleaning the silicon substrate of a standard cleaned silicon wafer (size: 40mm), the silicon wafer is placed on a heating plate and heated to 100℃ and held at that temperature. 9.8ml of 0.1mmol / L zinc acetate is added dropwise to the silicon wafer substrate and heated until the solution evaporates to dryness. The evaporated silicon wafer is then placed in a box furnace and annealed at 350℃ for 30min. This process converts zinc acetate to zinc oxide.
[0071] The resulting silicon wafer substrate with grown zinc oxide was then calcined in a box furnace at 500°C for 30 minutes to remove the surfactants adsorbed on the surface.
[0072] 10 mM, 15 mM, and 20 mM 2-methylimidazole and DMF / H2O (16 mL 3:1) mixed solvent were sequentially added to a 100 mL reaction vessel and sonicated for 5 min. The silicon wafer substrate with grown zinc oxide and the solutions of 10 mM, 15 mM, and 20 mM 2-methylimidazole and DMF / H2O mixed solvent were placed in a hydrothermal reaction vessel and sealed tightly. The sealed reaction vessel was placed in an oven and reacted at 90 °C for 24 h. After natural cooling, the reacted silicon wafer substrate was removed with tweezers and washed several times with ethanol.
[0073] Add 2.8 mg of platinum carbon to a mixed solution of 700 μL of naphthol and 300 μL of isopropanol, sonicate for 1.5 h, and mix thoroughly; coat the obtained mixture onto the surface of carbon paper and allow the solution to evaporate to dryness.
[0074] A 6 mol / L potassium hydroxide solution was prepared as the electrolyte for the air battery. The obtained ZIF-8 / silicon composite material and the obtained carbon paper were placed into an existing air battery mold, and then the prepared potassium hydroxide electrolyte was added. After standing for 2 hours, the battery discharge performance was tested.
[0075] like Figure 4 The image shown is a scanning electron microscope (SEM) planar view of the ZIF-8 / silicon composite electrode obtained in this embodiment. Figure 4 Figure (a) shows the morphology of the product after titration with 0.1 mM zinc acetate and conversion with 10 mM 2-methylimidazole; Figure 4 Figure (b) shows the morphology of the solution after titration with 0.1 mM zinc acetate and conversion with 15 mM 2-methylimidazole; Figure 4 Figure (c) shows the morphology of the product after titration with 0.1 mM zinc acetate followed by conversion with 20 mM 2-methylimidazole.
[0076] like Figure 8 As shown, the discharge time of the air battery obtained in this embodiment is longer than that of the blank silicon wafer, with the 10mM dimethylimidazole reaching a maximum of 414h.
[0077] like Figure 6 The image shows the XRD patterns of 0.1 mM zinc acetate after titration and conversion with 10 mM, 15 mM and 20 mM 2-methylimidazole in Example 2.
[0078] In this invention, a zinc oxide crystal structure was prepared on a silicon substrate using a solution growth method, and a ZIF-8 / silicon composite electrode was prepared by a solvothermal reaction using a DMF / H2O mixture. Based on this, the ZIF-8 / silicon composite silicon anode material was assembled with a platinum-carbon cathode and KOH solution in an air battery mold to construct a ZIF-8 / silicon air battery. During the discharge process of this silicon-based air battery, the ZIF-8 helps reduce the direct contact between the silicon substrate and water and the silicon dioxide passivation layer, inhibiting corrosion and passivation reactions, thereby extending the lifespan of the silicon air battery.
[0079] The present invention has the following advantages:
[0080] As described in the background section, silicon-air batteries are gradually coming into view. However, the bare silicon anode surface of silicon-air batteries will undergo passivation, corrosion and other side reactions under alkaline conditions, which greatly limits the further development of silicon-air batteries in the field of energy storage and conversion.
[0081] 1. This invention modifies the silicon anode of a silicon-air battery through a secondary growth and crystallization method. First, ZIF-8 material is grown in situ on the silicon surface. Due to the large specific surface area of ZIF-8, the zeolite imidazole ester framework (ZIF-8) / silicon composite has a large electrochemical specific surface area, which is beneficial for the contact between reactants and electrolyte. Second, because ZIF-8 material has small-pore, large-pore cage characteristics, it increases the OH- ions on the silicon surface. - The diffusion pore size also restricts the contact between water molecules and the silicon surface, allowing the zeolite imidazole ester framework (ZIF-8) / silicon composite material to increase the original hydrophobicity of the silicon wafer, thereby reducing ineffective corrosion on the silicon anode surface and protecting the silicon anode to a certain extent, thus extending the battery life.
[0082] 2. In the process of converting ZIF-8 in this invention, the content of ZIF-8 on the silicon surface is adjusted by controlling the mass of 2-methylimidazole; and the degree of crystallinity of ZIF-8 on the surface is adjusted by controlling the solvothermal reaction temperature.
[0083] 3. The present invention uses a secondary growth crystallization method to grow ZIF-8. Without adding binder, ZIF-8 crystals can still be grown tightly on the silicon anode surface and are not easy to fall off.
[0084] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.
Claims
1. A method for preparing a zeolite imidazole ester framework / silicon-air battery, characterized in that, Includes the following steps: 1) After cleaning the silicon substrate, place the silicon wafer on a heating plate and heat and keep it warm; 2) Add zinc acetate dropwise onto the silicon wafer substrate obtained in step 1), and heat until the solution evaporates to dryness; 3) Place the dried silicon wafer in a box furnace for annealing; In this step, place the dried silicon wafer in a box furnace and anneal at 300℃~350℃ for 30min~40min to convert zinc acetate seed crystals into zinc oxide crystals; 4) The silicon wafer substrate with zinc oxide grown in step 3) is calcined in a box furnace; In this step, the silicon wafer substrate with zinc oxide grown in step 3) is placed in a box furnace again and calcined at 450℃~500℃ for 30min~40min to remove the surfactant adsorbed on the surface. 5) Add 2-methylimidazole and DMF / H2O mixed solvent to the reaction vessel in sequence and sonicate. In this step, add 0.5mM~20mM 2-methylimidazole and 16mL~32mL DMF / H2O mixed solvent to the reaction vessel in sequence. The DMF / H2O is mixed in a ratio of 2:1~5:
1. Sonicate the reaction vessel containing the mixed solution for 5min~10min. 6) Place the silicon wafer substrate on which zinc oxide has been grown in step 4) and the mixed solution obtained in step 5) into a hydrothermal reactor, and seal the reactor. In this step, the silicon wafer substrate with zinc oxide grown in step 4) is placed upside down in a reactor of appropriate size, and the zeolite imidazole ester framework crystals grow downwards. 7) After sealing the reaction vessel from step 6), place it in an oven for a solvothermal reaction. In this step, after sealing the reaction vessel, place it in an oven at 70℃~100℃ for a solvothermal reaction for 24h~48h. 8) After the silicon wafer has cooled naturally, use tweezers to remove the reacted substrate and wash it several times with ethanol. 9) Add platinum carbon to a mixed solution of naphthol and isopropanol, and sonicate until fully mixed; in this step, add 2.8 mg to 5.6 mg of platinum carbon to a mixed solution of 700 μL to 1000 μL of naphthol and 300 μL to 500 μL of isopropanol, and sonicate for 1 h to 1.5 h until the mixture gradually becomes viscous; 10) Apply the mixture obtained in step 9) onto the surface of the composite carbon paper and allow the solution to evaporate to dryness; in this step, the composite carbon paper is selected as a three-layer structure consisting of a nickel mesh, a waterproof layer and carbon paper. 11) Prepare a potassium hydroxide solution as the electrolyte for a silicon-based air battery; in this step, the silicon-based air battery electrolyte is a 1~10 mol / L potassium hydroxide solution; 12) After loading the zeolite imidazole ester skeleton / silicon composite material obtained in step 8) and the carbon paper obtained in step 10) into the existing air battery mold, add the electrolyte obtained in step 11), let it stand for 2 hours, and then test the battery discharge.
2. The method for preparing a zeolite imidazole ester framework / silicon-air battery according to claim 1, characterized in that, In step 1), the silicon wafer has a diameter of 10mm to 80mm and a thickness of 200μm to 800μm, and the heating plate heats it to 70℃ to 120℃ and keeps it warm.
3. The method for preparing a zeolite imidazole ester framework / silicon-air battery according to claim 1, characterized in that, In step 2), 5 mL to 10 mL of 0.1 mmol / L to 1 mmol / L zinc acetate is added dropwise three times to the silicon wafer substrate obtained in step 1), and the solution is heated until it evaporates to dryness.
4. A zeolite imidazole ester framework / silicon-air battery, characterized in that, It is prepared by the method described in any one of claims 1-3 above.