Preparation method of anode-free tin-air battery with Fe-HHTP@Cu composite as current collector
By using Fe-HHTP@Cu composite material as the current collector, the problem of tin anode corrosion and uneven deposition in the anode-free tin-air battery was solved, and the stability and energy density of the tin-air battery were improved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- KUNMING UNIVERSITY
- Filing Date
- 2026-04-21
- Publication Date
- 2026-07-21
AI Technical Summary
In traditional tin-air batteries, the tin metal anode is prone to corrosion, resulting in uneven deposition during charging and discharging, which leads to dendrite growth and "dead tin" phenomenon, affecting the battery's capacity utilization and cycle stability.
Using Fe-HHTP@Cu composite material as the current collector, an anode-free tin-air battery system was constructed and an EC-MOF artificial interface layer was introduced to regulate tin deposition behavior and suppress uneven deposition and dendrite growth.
It effectively avoids tin anode corrosion, improves tin utilization, enhances tin deposition uniformity, and improves battery cycle stability and energy density.
Smart Images
Figure CN122436626A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of materials technology, and in particular to a method for preparing an anode-free tin-air battery using Fe-HHTP@Cu composite material as a current collector. Background Technology
[0002] With the continued growth of global energy demand, especially the rapid development of clean energy, energy storage technology has become a key approach to solving energy supply problems. Metal-air batteries, particularly tin-air batteries, have become increasingly important due to their high theoretical capacity (451.6 mAh g). -1 With its high efficiency and low cost, tin has shown great potential in large-scale energy storage. As an anode material, tin has a high hydrogen evolution overpotential and a moderate redox potential (-0.14 V vs. standard hydrogen electrode, SHE), making it an ideal choice for manufacturing high-efficiency batteries.
[0003] Tin-air batteries have a significantly higher theoretical energy density than traditional lithium batteries, giving them a clear advantage in high-energy-demand applications. However, traditional tin-air batteries face some challenges in practical applications. The tin anode is easily corroded and prone to uneven deposition during charging and discharging, leading to dendrite growth and the formation of "dead tin," which affects the battery's capacity utilization and cycle stability. In addition, the volume change and oxidation reaction of the tin anode also limit the battery's long-term stability. Summary of the Invention
[0004] The purpose of this invention is to provide a method for preparing an anode-free tin-air battery using Fe-HHTP@Cu composite material as the current collector. By constructing an anode-free tin-air battery system and introducing an EC-MOF artificial interface layer, the tin deposition behavior can be effectively controlled, overcoming the technical problems of traditional tin-air batteries in terms of corrosion, volume change, and uneven deposition.
[0005] The above-mentioned technical objective of the present invention is achieved through the following technical solution: A method for preparing an anode-free tin-air battery using Fe-HHTP@Cu composite material as the current collector includes the following steps: Preparation of S1 and Fe-HHTP@Cu composite materials: 2,3,6,7,10,11-hexahydroxytriphenyl and ferrous acetate were weighed and placed into a sample bottle. Deionized water was added to the sample bottle and the mixture was sonicated for 5-10 min to obtain solution I. Then, dimethylformamide was added to solution I and sonicated for another 5 min to obtain solution II. The solution was then placed in an oven and heated. After cooling, it was washed and dried to obtain Fe-HHTP powder. Fe-HHTP powder, conductive carbon black, and polyvinylidene fluoride were mixed in a certain mass ratio, and N-methylpyrrolidone solvent was added and stirred into a uniform slurry. The slurry was then coated onto the surface of a copper sheet and dried under vacuum to obtain the Fe-HHTP@Cu composite material. In the Fe-HHTP@Cu composite material, Fe-HHTP serves as an artificial interface protective layer for conductive metal-organic framework materials, which is used to regulate the nucleation and deposition behavior of tin and suppress uneven deposition, dendrite growth, and the "dead tin" phenomenon. S2. Preparation of electrolyte: Weigh the solid KOH into a beaker, add deionized water and stir to accelerate heat dissipation until the beaker wall is no longer hot. Then pour the KOH in the beaker into a volumetric flask and make up to volume. Then take an appropriate amount of KOH solution and solid SnO2 and stir until the solution becomes clear. Preparation of S3 and Pt / C cathodes: A certain amount of platinum carbon catalyst was weighed and placed in a beaker. Naphthol solution was first added to the beaker using a pipette, followed by isopropanol. The beaker containing the three substances was then placed in an ultrasonic bath for ultrasonic dissolution. The dissolved solution was then evenly coated onto carbon paper using a pipette and dried at room temperature to prepare the Pt / C cathode. S4. Assembly of anode-free tin-air battery: The Fe-HHTP@Cu composite material and Pt / C cathode obtained above are assembled on an air battery mold, and then the electrolyte is loaded into the electrolytic cell using a dropper to obtain an anode-free tin-air battery.
[0006] Furthermore, in S1, the molar ratio of 2,3,6,7,10,11-hexahydroxytriphenyl to ferrous acetate is 1.8 to 2.2.
[0007] Furthermore, in S1, the amount of 2,3,6,7,10,11-hexahydroxytriphenyl is 0.032~0.32 mmol, and the amount of ferrous acetate is 0.065~0.65 mmol.
[0008] Furthermore: In S1, solution II is placed in an oven and heated to a temperature of 70~90℃ for 15~25 hours.
[0009] Further: In S1, after solution II has cooled, wash it 1-2 times sequentially with anhydrous ethanol, acetone and deionized water.
[0010] Furthermore: In S1, the ratio of Fe-HHTP powder: conductive carbon black: polyvinylidene fluoride is 6~8:4~1:1~4.
[0011] Furthermore: In S1, the diameter of the copper sheet is 10~70 mm and the thickness is 0.01~0.1 mm; the Fe-HHTP@Cu composite material needs to be placed in a petri dish and dried in a vacuum environment at 40~55℃ for 10~12 hours.
[0012] Furthermore: In S2, the concentration of KOH is 2~6 mol / L, and the SnO2 in the solid SnO2... 2- The concentration is 0.1~0.4 mol / L.
[0013] Furthermore, in S3, the amount of the platinum-carbon catalyst is 2-5 mg, the amount of the naphthol solution is 600-800 μL, and the amount of the isopropanol is 200-400 μL.
[0014] The present invention also provides an anode-free tin-air battery, which is prepared by the preparation method described in any one of claims 1-9.
[0015] In summary, the present invention has the following beneficial effects: Firstly, the Fe-HHTP@Cu composite material of the present invention, which is used as a current collector in the anode-free tin-air battery, does not use pre-placed tin metal. Instead, it uses the current collector as a deposition substrate and achieves reversible deposition and dissolution of tin ions in the electrolyte during the charging and discharging process. This allows tin to exist in a dynamic form, which can not only effectively avoid the problem of anode corrosion, but also reduce the inactive mass in the battery system, improve the utilization rate of tin, and help improve the overall energy density of the battery. Secondly, the Fe-HHTP of the present invention has a highly ordered pore structure and a high specific surface area, which provides more active sites for the deposition of tin ions and significantly improves the uniformity of tin deposition. Compared with unmodified copper current collectors, the deposition of tin ions on Fe-HHTP@Cu current collectors is more stable, which alleviates the common problems of uneven deposition, dendrite growth and "dead tin" in anodes. Thirdly, by introducing a conductive metal-organic framework material as an artificial interface protective layer, this invention can make the deposition of tin ions more uniform, effectively suppress dendrite growth, and thus significantly improve the cycle stability and energy density of the battery. Attached Figure Description
[0016] Figure 1 This is a schematic diagram of the anode-free tin-air battery using the Fe-HHTP@Cu composite material as the current collector in this invention; Figure 2 This is the Fourier transform infrared (FTIR) spectrum of the Fe-HHTP@Cu composite material of the present invention. Figure 3 This is a planar electron microscope image of the Fe-HHTP@Cu composite material of the present invention; Figure 4 This is a cross-sectional electron microscope image of the Fe-HHTP@Cu composite material of the present invention; Figure 5 (a) shows a comparison of the cycle stability of an anode-free tin-air battery using Fe-HHTP@Cu composite material as the current collector and an anode-free tin-air battery using bare copper as the current collector at a current density of 0.1 mA / cm²; (b) shows a comparison of the cycle stability of an anode-free tin-air battery using Fe-HHTP@Cu composite material as the current collector and a bare copper current collector at a current density of 3 mA / cm². 2 Comparison of cycle stability between anode-free tin-air batteries using Fe-HHTP@Cu composite material as current collector and anode-free tin-air batteries using bare copper as current collector. Detailed Implementation
[0017] The present invention will be further described in detail below with reference to the accompanying drawings.
[0018] In the description of this invention, it should be understood that the terms "upper", "lower", "left", "right", "front", "rear", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They 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. Therefore, they should not be construed as limitations on this invention.
[0019] Example 1, referring to Figure 1-5 A method for preparing an anode-free tin-air battery using Fe-HHTP@Cu composite material as the current collector includes the following steps: Preparation of S1 and Fe-HHTP@Cu composite materials: 0.32 mmol of 2,3,6,7,10,11-hexahydroxytribenzene in a molar ratio of 2 and 0.64 mmol of ferrous acetate in a molar ratio of 2 were weighed and placed into a sample bottle. 19.5 ml of deionized water was added to the sample bottle and the mixture was ultrasonically treated for 10 min to obtain solution I. Then, 1.5 ml of dimethylformamide was added to solution I and sonicated for 5 min to obtain solution II. Then, it was placed in an oven and heated at 80 °C for 20 h until the reaction was complete. After cooling to room temperature, it was washed twice each with anhydrous ethanol, acetone and deionized water to remove impurities. The washed product was vacuum dried at 50 °C for 12 h to finally obtain Fe-HHTP powder. Weigh 40 mg of Fe-HHTP powder, 5 mg of conductive carbon black, and 5 mg of polyvinylidene fluoride and mix them in a mass ratio of 8:1:1 in a 25 ml beaker. Add N-methylpyrrolidone solvent and stir continuously until a uniform viscous slurry is formed. Polish copper sheets with a diameter of 10-70 mm and a thickness of 0.1 mm and ultrasonically clean them in acetone, anhydrous ethanol, and deionized water for 15 minutes each to remove surface impurities. Then coat the slurry onto the surface of the copper sheet and dry it in a vacuum environment at 40 °C for 10 h to finally obtain the Fe-HHTP@Cu composite material. Among them, Fe-HHTP in Fe-HHTP@Cu composite material serves as an artificial interface protective layer for conductive metal-organic framework materials, used to regulate the nucleation and deposition behavior of tin, and suppress uneven deposition, dendrite growth and "dead tin" phenomenon. S2. Preparation of electrolyte: Weigh the solid KOH and place it in a beaker. Add deionized water and stir to accelerate heat dissipation until the beaker wall is no longer hot. Then pour the KOH from the beaker into a volumetric flask and make up to volume. Next, take an appropriate amount of KOH solution and solid SnO2 and stir until the solution becomes clear. The concentration of KOH is 2~6 mol / L, and the concentration of solid SnO2 is... 2- The concentration is 0.1~0.4 mol / L; Preparation of S3 and Pt / C cathodes: Weigh 2-5 mg of platinum-carbon catalyst into a beaker. First, add 600-800 μL of naphthol solution to the beaker using a pipette. Then, add 200-400 μL of isopropanol. Next, place the beaker containing the three substances into an ultrasonic bath for ultrasonic dissolution. Then, use a pipette to evenly spread the dissolved solution onto carbon paper and dry it at room temperature to prepare the Pt / C cathode. S4. Assembly of anode-free tin-air battery: The Fe-HHTP@Cu composite material and Pt / C cathode obtained above are assembled on an air battery mold, and then the electrolyte is loaded into the electrolytic cell using a dropper to obtain an anode-free tin-air battery.
[0020] Example 2 differs from Example 1 in that: A method for preparing an anode-free tin-air battery using Fe-HHTP@Cu composite material as the current collector includes the following steps: Preparation of S1 and Fe-HHTP@Cu composite materials: 0.032 mmol of 2,3,6,7,10,11-hexahydroxytribenzene with a molar ratio of 1.8 and 0.058 mmol of ferrous acetate with a molar ratio of 1.8 were weighed and placed into a sample bottle. 1.95 ml of deionized water was added to the sample bottle and the mixture was sonicated for 5 min to obtain solution I. Then, 0.15 ml of dimethylformamide was added to solution I and sonicated for 5 min to obtain solution II. The solution II was then placed in an oven and heated at 80 °C for 24 h until the reaction was complete. After cooling to room temperature, the solution was washed twice each with anhydrous ethanol, acetone and deionized water to remove impurities. The washed product was then vacuum dried at 60 °C for 10 h to finally obtain Fe-HHTP powder. 35 mg Fe-HHTP powder, 10 mg conductive carbon black, and 5 mg polyvinylidene fluoride were mixed in a mass ratio of 7:2:1 and placed in a 25 ml beaker. N-methylpyrrolidone solvent was added and the mixture was stirred continuously until a uniform viscous slurry was formed. The surface of a copper sheet with a diameter of 10-70 mm and a thickness of 0.1 mm was then polished. The sheet was then ultrasonically cleaned in acetone, anhydrous ethanol, and deionized water for 15 minutes each to remove surface impurities. The slurry was then coated onto the surface of the copper sheet and dried in a vacuum environment at 50 °C for 12 hours to obtain the Fe-HHTP@Cu composite material. Among them, Fe-HHTP in Fe-HHTP@Cu composite material serves as an artificial interface protective layer for conductive metal-organic framework materials, used to regulate the nucleation and deposition behavior of tin, and suppress uneven deposition, dendrite growth and "dead tin" phenomenon.
[0021] like Figure 2 As shown, compared with the bare Cu substrate, Fe-HHTP@Cu exhibits obvious C–C, C–O and C–OH characteristic absorption peaks in the spectrum, proving the synthesis of Fe-HHTP; like Figure 3 , Figure 4 As shown, by observing the microstructure of the surface and cross-section of the Fe-HHTP@Cu composite material using SEM, it can be found that the Fe-HHTP film has been successfully grown on the copper sheet. Figure 5 Figure (a) shows a comparison of the cycle stability of an anode-free tin-air battery using Fe-HHTP@Cu composite material as the current collector and an anode-free tin-air battery using bare copper as the current collector at a current density of 0.1 mA / cm⁻². The anode-free tin-air battery using Fe-HHTP@Cu composite material as the current collector exhibits better cycle stability, smaller voltage fluctuations, and a longer charge-discharge time. This result indicates that Fe-HHTP@Cu composite material has higher stability and a longer service life, making it suitable for long-term use. Figure 5 (b) is a comparison of the cycle stability of an anode-free tin-air battery using Fe-HHTP@Cu composite material as the current collector and an anode-free tin-air battery using bare copper as the current collector at a current density of 3 mA / cm⁻². Figure 5(a) In comparison, at a current density of 3 mA / cm-², the anode-free tin-air battery with Fe-HHTP@Cu composite material as the current collector maintains a relatively stable voltage output during long-term charge-discharge cycles, while the anode-free tin-air battery assembled with bare copper exhibits obvious voltage decay and poor cycle stability. This further demonstrates the excellent performance and longer lifespan of Fe-HHTP@Cu composite material as a current collector in anode-free tin-air batteries at higher current densities.
[0022] This specific embodiment is merely an explanation of the present invention and is not intended to limit the invention. After reading this specification, those skilled in the art can make inventive modifications to this embodiment as needed, but as long as they are within the scope of the claims of the present invention, they are protected by patent law.
Claims
1. A method for preparing an anode-free tin-air battery using Fe-HHTP@Cu composite material as the current collector, characterized in that, Includes the following steps: Preparation of S1 and Fe-HHTP@Cu composite materials: 2,3,6,7,10,11-hexahydroxytriphenyl and ferrous acetate were weighed and placed into a sample bottle. Deionized water was added to the sample bottle and the mixture was sonicated for 5-10 min to obtain solution I. Then, dimethylformamide was added to solution I and sonicated for another 5 min to obtain solution II. The solution was then placed in an oven and heated. After cooling, it was washed and dried to obtain Fe-HHTP powder. Fe-HHTP powder, conductive carbon black, and polyvinylidene fluoride were mixed in a certain mass ratio, and N-methylpyrrolidone solvent was added and stirred into a uniform slurry. The slurry was then coated onto the surface of a copper sheet and dried under vacuum to obtain the Fe-HHTP@Cu composite material. In the Fe-HHTP@Cu composite material, Fe-HHTP serves as an artificial interface protective layer for conductive metal-organic framework materials, which is used to regulate the nucleation and deposition behavior of tin and suppress uneven deposition, dendrite growth, and the "dead tin" phenomenon. S2. Preparation of electrolyte: Weigh the solid KOH into a beaker, add deionized water and stir to accelerate heat dissipation until the beaker wall is no longer hot. Then pour the KOH in the beaker into a volumetric flask and make up to volume. Then take an appropriate amount of KOH solution and solid SnO2 and stir until the solution becomes clear. Preparation of S3 and Pt / C cathodes: A certain amount of platinum carbon catalyst was weighed and placed in a beaker. Naphthol solution was first added to the beaker using a pipette, followed by isopropanol. The beaker containing the three substances was then placed in an ultrasonic bath for ultrasonic dissolution. The dissolved solution was then evenly coated onto carbon paper using a pipette and dried at room temperature to prepare the Pt / C cathode. S4. Assembly of anode-free tin-air battery: The Fe-HHTP@Cu composite material and Pt / C cathode obtained above are assembled on an air battery mold, and then the electrolyte is loaded into the electrolytic cell using a dropper to obtain an anode-free tin-air battery.
2. The method for preparing an anode-free tin-air battery using Fe-HHTP@Cu composite material as a current collector according to claim 1, characterized in that: In S1, the molar ratio of 2,3,6,7,10,11-hexahydroxytriphenyl to ferrous acetate is 1.8 to 2.
2.
3. The method for preparing an anode-free tin-air battery using Fe-HHTP@Cu composite material as a current collector according to claim 1, characterized in that: The amount of 2,3,6,7,10,11-hexahydroxytriphenyl used is 0.032~0.32 mmol, and the amount of ferrous acetate used is 0.065~0.65 mmol.
4. The method for preparing an anode-free tin-air battery using Fe-HHTP@Cu composite material as a current collector according to claim 1, characterized in that: In S1, the heating temperature of the oven is 70~90℃, and the heating time is 15~25h.
5. The method for preparing an anode-free tin-air battery using Fe-HHTP@Cu composite material as a current collector according to claim 1, characterized in that: In S1, the washing process involves washing with anhydrous ethanol, acetone, and deionized water 1-2 times each in sequence.
6. The method for preparing an anode-free tin-air battery using Fe-HHTP@Cu composite material as a current collector according to claim 1, characterized in that: In S1, the ratio of Fe-HHTP powder: conductive carbon black: polyvinylidene fluoride is 6~8:4~1:1~4.
7. The method for preparing an anode-free tin-air battery using Fe-HHTP@Cu composite material as a current collector according to claim 1, characterized in that: In S1, the copper sheet has a diameter of 10~70 mm and a thickness of 0.01~0.1 mm; the Fe-HHTP@Cu composite material needs to be placed in a petri dish and dried in a vacuum environment at 40~55℃ for 10~12 hours.
8. The method for preparing an anode-free tin-air battery using Fe-HHTP@Cu composite material as a current collector according to claim 1, characterized in that: In S2, the concentration of KOH is 2~6 mol / L, and the SnO2 in the solid SnO2... 2- The concentration is 0.1~0.4 mol / L.
9. The method for preparing an anode-free tin-air battery using Fe-HHTP@Cu composite material as a current collector according to claim 1, characterized in that: In S3, the amount of platinum-carbon catalyst used is 2-5 mg, the amount of naphthol solution used is 600-800 μL, and the amount of isopropanol used is 200-400 μL.
10. A non-anode tin-air battery, characterized in that, It is prepared by the preparation method according to any one of claims 1-9.