A method for preparing and applying a polypyrrole-derived carbon nanotube-modified zinc anode.

Abstract

This invention discloses a method for preparing and applying polypyrrole-derived carbon nanotubes (PPNTs) modified zinc anodes, belonging to the field of electrochemical energy storage technology. The purpose of this invention is to solve the problems of short-circuit failure and limited lifespan caused by dendrite growth, hydrogen evolution, and corrosion side reactions in aqueous zinc-ion batteries during practical applications. The method includes: 1. Preparing a methyl orange solution; 2. Adding pyrrole monomer and p-toluenesulfonic acid to the methyl orange solution to obtain a mixed solution; 3. Magnetically stirring a ferric chloride solution under ice bath conditions for a period of time, then adding it dropwise to the mixed solution for reaction; 4. High-temperature calcination; 5. Preparing a slurry of polypyrrole-derived carbon nanotubes and coating it onto the surface of the zinc anode. This invention benefits from the higher interfacial stability and effective nucleation sites for nitrogen and sulfur doping in polypyrrole-derived carbon nanotube-modified zinc anodes, enabling the modified zinc anodes to withstand higher current densities and deposition capacities. It has the advantages of long cycle life and good stability, and the process is simple, possessing high industrialization potential.

Description

Technical Field

[0001] This invention belongs to the field of electrochemical energy storage technology, specifically relating to a method for preparing and applying a polypyrrole-derived carbon nanotube-modified zinc anode. Background Technology

[0002] Zinc anodes are widely used in energy storage devices such as aqueous zinc-ion batteries and zinc-air batteries due to their high theoretical specific capacity, low cost, and environmental friendliness. However, the use of zinc anodes faces a series of challenges, especially during charge and discharge processes, including dendrite growth, hydrogen evolution, and corrosion side reactions, which severely limit their practical application. Zinc dendrite growth can penetrate the electrolyte membrane, causing a short circuit; hydrogen evolution consumes charge and leads to gas accumulation within the battery, affecting its energy efficiency and safety. Furthermore, corrosion side reactions in the electrolyte accelerate the degradation of the zinc anode, reduce cycle stability, and ultimately lead to battery performance deterioration. Therefore, there is an urgent need to develop an effective zinc anode modification technology to improve its long-term performance and stability.

[0003] Therefore, this invention proposes a method for preparing a zinc anode modified with polypyrrole-derived carbon nanotubes. The modified zinc anode can effectively suppress the growth of zinc dendrites, hydrogen evolution reaction, and corrosion side reactions; thanks to higher interfacial stability and more effective nucleation sites, the modified zinc anode can withstand higher current densities and deposition capacity. Furthermore, the preparation method of the modified zinc anode is relatively simple and can be achieved through conventional coating processes, ensuring coating uniformity while reducing production costs. Summary of the Invention

[0004] The purpose of this invention is to solve the problems of short-circuit failure and limited lifespan caused by dendrite growth, hydrogen evolution and corrosion side reactions of zinc anode in the practical application of aqueous zinc-ion batteries, and to provide a method for preparing and applying polypyrrole-derived carbon nanotube-modified zinc anodes.

[0005] A method for preparing a zinc anode modified with polypyrrole-derived carbon nanotubes is specifically carried out according to the following steps:

[0006] 1. Add methyl orange to deionized water, and then stir under water bath heating until the methyl orange is completely dissolved to obtain a methyl orange solution;

[0007] 2. Add pyrrole monomer and p-toluenesulfonic acid to the methyl orange solution and stir magnetically to obtain a mixed solution;

[0008] 3. Add ferric chloride to deionized water and stir magnetically to obtain a ferric chloride solution; stir the ferric chloride solution magnetically for a period of time under ice bath conditions, then add it dropwise to the mixed solution and stir continuously for a period of time under ice-water bath conditions to obtain solid reactant I; wash and dry solid reactant I to obtain solid reactant II.

[0009] IV. Transfer solid reactant II to a tube furnace, heat it to the calcination temperature under an inert gas atmosphere, calcine it at the calcination temperature for a period of time, and grind it into particles after calcination to obtain polypyrrole-derived carbon tubes.

[0010] 5. Disperse the polypyrrole-derived carbon nanotubes and binder in a solvent to obtain a slurry; coat the slurry onto the surface of the zinc anode and dry it to obtain a polypyrrole-derived carbon nanotube-modified zinc anode.

[0011] The beneficial effects of this invention are:

[0012] I. This invention uses pyrrole as a precursor to prepare carbon nanotubes; the carbon nanotubes have abundant defects and a large number of nitrogen and sulfur doped structures; among them, the doped nitrogen and sulfur elements serve as effective zinc-loving sites, which can effectively enrich zinc ions; combined with the hydrophobic properties of carbon materials, the carbon nanotube materials prepared by this method help to reduce the direct contact between water molecules and zinc anodes, thereby inhibiting hydrogen evolution and corrosion side reactions.

[0013] Second, the three-dimensional cross-linked network formed by carbon nanotubes can provide a large number of effective nucleation sites for zinc ion deposition. Combined with the nucleation sites at the interface between the zinc anode and the carbon nanotube coating, the modified zinc anode can achieve long-term stable cycling under greater areal capacity and current density, thus extending the service life of the zinc anode.

[0014] III. Zn / / Zn symmetric cells assembled using polypyrrole-derived carbon nanotubes as the negative electrode can achieve 20 mA / cm². 2 It can cycle stably for more than 1500 hours at high current density, far exceeding the lifespan of the original symmetrical battery assembled with zinc anode.

[0015] Fourth, the polypyrrole-derived carbon nanotube-modified zinc anode prepared by this invention has the advantages of long cycle life and good stability, and the coating preparation process is simple, which has industrialization prospects.

[0016] This invention provides a polypyrrole-derived carbon nanotube-modified zinc anode for use as the anode in aqueous zinc-ion batteries. Attached Figure Description

[0017] Figure 1 Scanning electron microscope image of the polypyrrole-derived carbon nanotubes prepared in Example 1;

[0018] Figure 2 Here is the S2p high-resolution X-ray photoelectron spectrum of the polypyrrole-derived carbon nanotubes prepared in Example 1;

[0019] Figure 3 A symmetric cell assembled using an unmodified zinc anode and a zinc anode modified with polypyrrole-derived carbon nanotubes prepared in Example 1 was tested at 20 mA / cm². 2 1mAh / cm 2Time-voltage curve under test conditions;

[0020] Figure 4 Scanning electron microscope image of the polypyrrole-derived carbon nanotubes prepared in Example 2;

[0021] Figure 5 Here is the S2p high-resolution X-ray photoelectron spectrum of the polypyrrole-derived carbon nanotubes prepared in Example 2;

[0022] Figure 6 To test the symmetric cell assembled using the polypyrrole-derived carbon nanotubes modified zinc anode prepared in Example 2 at 20 mA / cm 2 1mAh / cm 2 Time-voltage curve under test conditions;

[0023] Figure 7 A scanning electron microscope image of the polypyrrole-derived carbon nanotubes prepared in Example 3;

[0024] Figure 8 Scanning electron microscope image of the polypyrrole-derived carbon nanotubes prepared in Example 4;

[0025] Figure 9 Scanning electron microscope image of the polypyrrole-derived carbon nanotubes prepared in Example 5. Detailed Implementation

[0026] Specific Implementation Method 1: This implementation method describes a method for preparing a zinc anode modified with polypyrrole-derived carbon nanotubes, which is specifically completed according to the following steps:

[0027] 1. Add methyl orange to deionized water, and then stir under water bath heating until the methyl orange is completely dissolved to obtain a methyl orange solution;

[0028] 2. Add pyrrole monomer and p-toluenesulfonic acid to the methyl orange solution and stir magnetically to obtain a mixed solution;

[0029] 3. Add ferric chloride to deionized water and stir magnetically to obtain a ferric chloride solution; stir the ferric chloride solution magnetically for a period of time under ice bath conditions, then add it dropwise to the mixed solution and stir continuously for a period of time under ice-water bath conditions to obtain solid reactant I; wash and dry solid reactant I to obtain solid reactant II.

[0030] IV. Transfer solid reactant II to a tube furnace, heat it to the calcination temperature under an inert gas atmosphere, calcine it at the calcination temperature for a period of time, and grind it into particles after calcination to obtain polypyrrole-derived carbon tubes.

[0031] 5. Disperse the polypyrrole-derived carbon nanotubes and binder in a solvent to obtain a slurry; coat the slurry onto the surface of the zinc anode and dry it to obtain a polypyrrole-derived carbon nanotube-modified zinc anode.

[0032] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the concentration of the methyl orange solution in step one is 15 mmol / L to 30 mmol / L; and the water bath heating temperature in step one is 60℃ to 80℃. All other steps are the same as in Specific Implementation Method One.

[0033] Specific Implementation Method Three: This implementation method differs from Specific Implementation Method One or Two in the following ways: the volume ratio of pyrrole monomer to methyl orange solution in step two is (300 μL–400 μL):(80 mL–120 mL); the mass ratio of p-toluenesulfonic acid to methyl orange solution in step two is (120 mg–150 mg):(80 mL–120 mL); the magnetic stirring speed in step two is 800 r / min–1000 r / min, and the magnetic stirring time is 60 min–90 min. Other steps are the same as in Specific Implementation Method One or Two.

[0034] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that: the concentration of the ferric chloride solution in step three is 40 mmol / L to 60 mmol / L; the magnetic stirring speed in step three is 500 r / min to 1000 r / min, and the magnetic stirring time is 10 min to 30 min. Other steps are the same as in Specific Implementation Methods One to Three.

[0035] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods One to Four in that: the ice bath conditions described in step three are achieved using an ice-water mixture, with an actual temperature of 0°C; the time for magnetically stirring the ferric chloride solution under ice bath conditions in step three is 1 to 2 hours; and the volume ratio of the ferric chloride solution to the methyl orange solution in the mixed solution in step three is (15 mL to 25 mL):(80 mL to 120 mL). Other steps are the same as in Specific Implementation Methods One to Four.

[0036] Specific Implementation Method Six: This implementation method differs from Specific Implementation Methods One to Five in the following ways: In step three, the stirring speed under ice-water bath conditions is 700 r / min to 900 r / min, and the stirring time is 24 h to 36 h; in step three, deionized water is used to wash solid reactant I until the washing solution is colorless; the drying temperature in step three is 70℃ to 90℃, and the drying time is 8 h to 10 h. Other steps are the same as in Specific Implementation Methods One to Five.

[0037] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One through Six in that: the inert gas mentioned in step four is nitrogen, argon, helium, or a mixture of these gases; the heating rate mentioned in step four is 2℃ / min to 10℃ / min; the calcination temperature mentioned in step four is 700℃ to 900℃, and the calcination time is 60min to 100min. Other steps are the same as in Specific Implementation Methods One through Six.

[0038] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Methods One to Seven in that: the solvent mentioned in step five is one or a mixture of several of N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, dichloromethane, and ethanol; the binder mentioned in step five is one or a mixture of several of polyvinylidene fluoride, polyacrylic acid, sodium carboxymethyl cellulose, styrene-butadiene rubber, chitosan, and polyurethane; the mass ratio of polypyrrole-derived carbon nanotubes to binder mentioned in step five is (8-9):(1-2); the mass fraction of polypyrrole-derived carbon nanotubes in the slurry mentioned in step five is 20%-50%. Other steps are the same as in Specific Implementation Methods One to Seven.

[0039] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods One to Eight in that: the drying temperature in step five is 60℃~80℃; and the thickness of the polypyrrole-derived carbon nanotubes in the polypyrrole-derived carbon nanotube-modified zinc anode in step five is 5μm~30μm. Other steps are the same as in Specific Implementation Methods One to Eight.

[0040] Specific Implementation Method 10: This implementation method describes the use of a polypyrrole-derived carbon nanotube-modified zinc anode as the anode of an aqueous zinc-ion battery.

[0041] The beneficial effects of the present invention are verified using the following embodiments:

[0042] Example 1: A method for preparing a zinc anode modified with polypyrrole-derived carbon nanotubes, specifically completed according to the following steps:

[0043] 1. Add methyl orange to deionized water, and then stir under water bath heating at 80°C until the methyl orange is completely dissolved to obtain a methyl orange solution;

[0044] The concentration of the methyl orange solution mentioned in step one is 15 mmol / L;

[0045] 2. Add 350 μL of pyrrole monomer and 140 mg of p-toluenesulfonic acid to 100 mL of methyl orange solution, and stir magnetically at 800 r / min for 60 min to obtain a mixed solution;

[0046] 3. Add ferric chloride to deionized water and then magnetically stir at 1000 r / min for 30 min to obtain a ferric chloride solution. Stir the ferric chloride solution magnetically in an ice bath at 0°C for 1 h at 800 r / min. Then, add 20 mL of the ferric chloride solution dropwise to the mixed solution obtained in step 2. Continue magnetic stirring at 800 r / min in an ice-water bath for 24 h to obtain solid reactant I. Wash solid reactant I three times with deionized water and then dry at 70°C for 10 h to obtain solid reactant II.

[0047] The concentration of the ferric chloride solution mentioned in step three is 50 mmol / L;

[0048] IV. Transfer solid reactant II to a tube furnace, heat it to 800°C under a nitrogen atmosphere, calcine it at 800°C for 80 min, and grind it into particles after calcination to obtain polypyrrole-derived carbon tubes.

[0049] The heating rate described in step four is 5°C / min;

[0050] 5. Disperse 45 mg of polypyrrole-derived carbon nanotubes and polyvinylidene fluoride into 140 μL of N-methylpyrrolidone to obtain a slurry; coat the slurry onto the zinc anode surface with a thickness of 100 μm after removing the oxide layer, adjust the coating thickness of the coating device to 300 μm, and dry at 80 °C for 12 h to obtain a polypyrrole-derived carbon nanotube-modified zinc anode;

[0051] The mass ratio of polypyrrole-derived carbon nanotubes to polyvinylidene fluoride mentioned in step five is 9:1;

[0052] In step five, the zinc anode with a 100μm oxide layer is removed by polishing it with sandpaper until it is shiny to remove the oxide layer, thus obtaining a zinc anode with a 100μm oxide layer removed.

[0053] Figure 1 Scanning electron microscope image of the polypyrrole-derived carbon nanotubes prepared in Example 1;

[0054] from Figure 1 As can be seen from the above, the polypyrrole-derived carbon nanotubes prepared in Example 1 have a distinct tubular structure.

[0055] Figure 2 Here is the S2p high-resolution X-ray photoelectron spectrum of the polypyrrole-derived carbon nanotubes prepared in Example 1;

[0056] from Figure 2 As can be seen from the data, the polypyrrole-derived carbon nanotubes prepared in Example 1 have a significant sulfur doping signal.

[0057] The symmetrical battery assembled with a zinc anode modified by polypyrrole-derived carbon nanotubes was prepared using Example 1, specifically by following these steps:

[0058] ① The polypyrrole-derived carbon tube modified zinc anode prepared in Example 1 is punched into a disc with a diameter of 14 mm using a punching machine, which serves as the electrode sheet for the symmetrical battery;

[0059] ② The glass fiber is punched into round sheets with a diameter of 16mm using a punching machine to serve as a diaphragm;

[0060] ③ The electrolyte is a 2 mol / L zinc sulfate solution;

[0061] ④ Place the battery electrode, separator, and 70 μL of electrolyte into the negative terminal casing of the button cell in sequence. After wetting the separator, add the electrode, stainless steel gasket, spring contact, and positive terminal casing of the button cell. Then, use a sealing machine at 50 kg / cm². 2 Encapsulated button-shaped symmetrical cells under pressure.

[0062] Figure 3 A symmetric cell assembled using an unmodified zinc anode and a zinc anode modified with polypyrrole-derived carbon nanotubes prepared in Example 1 was tested at 20 mA / cm². 2 1mAh / cm 2 Time-voltage curve under test conditions;

[0063] from Figure 3 It can be seen that, compared with the symmetric battery composed of untreated pure zinc sheets, the symmetric battery composed of the zinc anode modified with polypyrrole-derived carbon nanotubes prepared in Example 1 has a significantly improved cycle life, with stable cycling exceeding 1500h. The polarization voltage did not fluctuate significantly during the entire cycle, which strongly proves the cycle stability of the modified zinc anode.

[0064] Example 2: The difference between this example and Example 1 is that in step two, 350 μL of pyrrole monomer was added to 100 mL of methyl orange solution, and the mixture was magnetically stirred at 800 r / min for 60 min to obtain a mixed solution. All other steps and parameters were the same as in Example 1.

[0065] Figure 4 Scanning electron microscope image of the polypyrrole-derived carbon nanotubes prepared in Example 2;

[0066] from Figure 4 As can be seen from the results, the morphology of polypyrrole-derived carbon nanotubes prepared without the participation of p-toluenesulfonic acid in the synthesis did not change significantly, proving that p-toluenesulfonic acid does not affect the morphology of carbon nanotubes.

[0067] Figure 5 Here is the S2p high-resolution X-ray photoelectron spectrum of the polypyrrole-derived carbon nanotubes prepared in Example 2;

[0068] from Figure 5 As can be seen from the data, no sulfur doping signal was detected in the polypyrrole-derived carbon nanotubes prepared in Example 2 without p-toluenesulfonic acid, proving that p-toluenesulfonic acid is indispensable for sulfur doping in the carbon nanotube preparation process.

[0069] The symmetrical battery assembled with a zinc anode modified with polypyrrole-derived carbon nanotubes was prepared using Example 2, and was specifically carried out according to the following steps:

[0070] ① The zinc negative electrode with carbon nanotube coating prepared in Example 2 is punched into a circular sheet with a diameter of 14 mm using a punching machine, which serves as the electrode sheet for the symmetrical battery;

[0071] ② The glass fiber is punched into round sheets with a diameter of 16mm using a punching machine to serve as a diaphragm;

[0072] ③ The electrolyte is a 2 mol / L zinc sulfate solution;

[0073] ④ Place the battery electrode, separator, and 70 μL of electrolyte into the negative terminal casing of the button cell in sequence. After wetting the separator, add the electrode, stainless steel gasket, spring contact, and positive terminal casing of the button cell. Then, use a sealing machine at 50 kg / cm². 2 Encapsulated button-shaped symmetrical cells under pressure.

[0074] Figure 6 To test the symmetric cell assembled using the polypyrrole-derived carbon nanotubes modified zinc anode prepared in Example 2 at 20 mA / cm 2 1mAh / cm 2 Time-voltage curve under test conditions;

[0075] from Figure 6 It can be seen that the cycle life of the symmetric cell composed of a polypyrrole-derived carbon nanotube-modified zinc anode without p-toluenesulfonic acid is less than 1200h. The cycle life is better than that of the bare zinc electrode under the same conditions, but worse than that of the symmetric cell composed of a carbon nanotube-modified zinc anode synthesized with p-toluenesulfonic acid. This proves the important role of p-toluenesulfonic acid in carbon nanotube-modified zinc anodes.

[0076] Example 3: The difference between this example and Example 2 is as follows: In step three, ferric chloride is added to deionized water and then magnetically stirred at 1000 r / min for 30 min to obtain a ferric chloride solution; 20 mL of the ferric chloride solution is added dropwise to the mixed solution obtained in step two under magnetic stirring at 800 r / min, and then magnetically stirred continuously at 800 r / min for 24 h to obtain solid reactant I; solid reactant I is washed three times with deionized water and then dried at 70°C for 10 h to obtain solid reactant II; other steps and parameters are the same as in Example 2.

[0077] Figure 7 A scanning electron microscope image of the polypyrrole-derived carbon nanotubes prepared in Example 3;

[0078] from Figure 7 As can be seen, under conditions without an ice bath, the morphology of the polypyrrole-derived carbon nanotubes prepared is between that of a bulk structure and a carbon nanotube structure.

[0079] Example 4: The difference between this example and Example 2 is that the concentration of the methyl orange solution in step one is 10 mmol / L. Other steps and parameters are the same as in Example 2.

[0080] Figure 8 Scanning electron microscope image of the polypyrrole-derived carbon nanotubes prepared in Example 4;

[0081] from Figure 8 As can be seen, when the concentration of methyl orange is low, the polypyrrole-derived carbon nanotubes prepared have a lot of spherical impurities.

[0082] Example 5: The difference between this example and Example 2 is that the concentration of the methyl orange solution in step one is 40 mmol / L. All other steps and parameters are the same as in Example 2.

[0083] Figure 9 Scanning electron microscope image of the polypyrrole-derived carbon nanotubes prepared in Example 5;

[0084] from Figure 9 As can be seen, when the concentration of methyl orange is too high, the polypyrrole-derived carbon nanotubes prepared have a deformed morphology of multiple tubular hybrids.

Claims

1. A method for preparing a zinc anode modified with polypyrrole-derived carbon nanotubes, characterized in that... The preparation method is specifically completed according to the following steps: I. methyl orange is added into deionized water, and then stirred under water bath heating until the methyl orange is completely dissolved to obtain a methyl orange solution; The concentration of the methyl orange solution in step I is 15 mmol / L to 30 mmol / L; II. pyrrole monomer and p-toluenesulfonic acid are added into the methyl orange solution, and then magnetically stirred to obtain a mixed solution; The volume ratio of the pyrrole monomer to the methyl orange solution in step II is (300 μL to 400 μL) to (80 mL to 120 mL); The mass / volume ratio of the p-toluenesulfonic acid to the methyl orange solution in step II is (120 mg to 150 mg) to (80 mL to 120 mL); III. ferric chloride is added into deionized water, and then magnetically stirred to obtain a ferric chloride solution; The ferric chloride solution is magnetically stirred in an ice bath for a period of time, and then added dropwise into the mixed solution, and then continuously stirred in an ice water bath for a period of time to obtain solid reactant I; The solid reactant I is washed and dried to obtain solid reactant II; The ice bath condition in step III is achieved by using an ice water mixture, and the actual temperature is 0 ℃; IV. the solid reactant II is transferred into a tube furnace, heated to a calcination temperature under an inert gas atmosphere, calcined at the calcination temperature for a period of time, and then ground into particles to obtain polypyrrole derivative carbon tubes; The calcination temperature in step IV is 700 ℃ to 900 ℃, and the calcination time is 60 min to 100 min; V. the polypyrrole derivative carbon tubes and a binder are dispersed into a solvent to obtain a slurry; and the slurry is coated on the surface of a zinc negative electrode and dried to obtain a polypyrrole derivative carbon tube modified zinc negative electrode.

2. The method for preparing polypyridine derivative carbon tube modified zinc negative electrode according to claim 1, characterized in that The water bath heating temperature in step I is 60 ℃ to 80 ℃.

3. The method for preparing a polypyrrole-derived carbon nanotube-modified zinc anode according to claim 1, characterized in that... The magnetic stirring speed in step II is 800 r / min to 1000 r / min, and the magnetic stirring time is 60 min to 90 min.

4. The method for preparing a polypyrrole-derived carbon nanotube-modified zinc anode according to claim 1, characterized in that... The concentration of the ferric chloride solution in step III is 40 mmol / L to 60 mmol / L; the magnetic stirring speed in step III is 500 r / min to 1000 r / min, and the magnetic stirring time is 10 min to 30 min.

5. The method for preparing a polypyrrole-derived carbon nanotube-modified zinc anode according to claim 1, characterized in that... The ferric chloride solution is magnetically stirred in the ice bath for 1 h to 2 h in step III; and the volume ratio of the ferric chloride solution to the methyl orange solution in the mixed solution is (15 mL to 25 mL) to (80 mL to 120 mL) in step III.

6. The method for preparing a polypyrrole-derived carbon nanotube-modified zinc anode according to claim 1, characterized in that... The continuous stirring speed in the ice water bath in step III is 700 r / min to 900 r / min, and the continuous stirring time is 24 h to 36 h; deionized water is used to wash the solid reactant I in step III until the washing solution is colorless; and the drying temperature in step III is 70 ℃ to 90 ℃, and the drying time is 8 h to 10 h.

7. The method for preparing a polypyrrole-derived carbon nanotube-modified zinc anode according to claim 1, characterized in that... The inert gas in step IV is nitrogen, argon, helium or a mixture of the above; and the heating rate in step IV is 2 ℃ / min to 10 ℃ / min.

8. The method for preparing a polypyrrole-derived carbon nanotube-modified zinc anode according to claim 1, characterized in that... The solvent in step five is one or a mixture of several of N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, dichloromethane and ethanol; the binder in step five is one or a mixture of several of polyvinylidene fluoride, polyacrylic acid, sodium carboxymethyl cellulose, styrene-butadiene rubber, chitosan and polyurethane; the mass ratio of the polypyrrole derivative carbon tube to the binder in step five is (8~9):(1~2); the mass fraction of the polypyrrole derivative carbon tube in the slurry in step five is 20%~50%.

9. The method for preparing a polypyrrole-derived carbon nanotube-modified zinc anode according to claim 1, characterized in that... The drying temperature in step five is 60℃~80℃; the thickness of the polypyrrole derivative carbon tube in the polypyrrole derivative carbon tube modified zinc negative electrode in step five is 5μm~30μm.

10. The use of a polypyrole derivative carbon nanotube modified zinc anode prepared by the method of claim 1, wherein the polypyrole derivative carbon nanotube modified zinc anode is used as a zinc anode for a battery. A polypyrrole derivative carbon tube modified zinc negative electrode is used as a negative electrode of a water-based zinc ion battery.

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