Preparation method and application of polypyrrole derived carbon tube modified zinc negative electrode

Abstract

The invention discloses a preparation method and application of a polypyrrole derived carbon tube modified zinc negative electrode, and belongs to the technical field of electrochemical energy storage. The invention aims to solve the problems of short circuit failure and limited service life caused by dendritic crystal growth, hydrogen evolution and corrosion side reaction of a zinc negative electrode in the actual application process of the current aqueous zinc ion battery. The method comprises the following steps: 1, preparing a methyl orange solution; 2, adding a pyrrole monomer and p-toluenesulfonic acid into the methyl orange solution to obtain a mixed solution; 3, magnetically stirring the ferric chloride solution for a period of time under an ice bath condition, and dropwise adding the ferric chloride solution into the mixed solution to react; 4, high-temperature calcination; and 5, preparing the polypyrrole derivative carbon tube into slurry, and coating the surface of the zinc negative electrode with the slurry. The polypyrrole derived carbon tube modified zinc negative electrode has higher interface stability and nitrogen and sulfur doped effective nucleation sites, so that the modified zinc negative electrode can bear higher current density and deposition capacity. The preparation method has the advantages of long cycle life and good stability, is simple in process and has a relatively high industrialization prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of electrochemical energy storage, and specifically relates to a preparation method and application of a polypyrrole-derived carbon tube-modified zinc negative electrode. Background Art

[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 the charging and discharging process, there are problems such as dendrite growth, hydrogen evolution and corrosion side reactions, which seriously limit their practical application. The growth of zinc dendrites may penetrate the electrolyte membrane and cause battery short circuit; the hydrogen evolution reaction consumes charge and causes gas accumulation in the battery, thereby affecting its energy efficiency and safety. In addition, the corrosion side reactions of the zinc anode in the electrolyte will accelerate its degradation, reduce the cycle stability, and ultimately lead to the deterioration of battery performance. Therefore, it is urgent to develop an effective zinc anode modification technology to improve its long-term performance and stability.

[0003] Therefore, the present invention proposes a method for preparing a polypyrrole-derived carbon tube-modified zinc negative electrode. The modified zinc negative electrode can effectively inhibit the growth of zinc dendrites, hydrogen evolution reaction and corrosion side reactions; thanks to higher interface stability and more effective nucleation sites, the modified zinc negative electrode can withstand higher current density and deposition capacity. In addition, the preparation method of the modified zinc negative electrode is relatively simple and can be achieved through conventional coating processes, which not only ensures the uniformity of the coating, but also reduces production costs. Summary of the invention

[0004] The purpose of the present invention is to solve the problems of short-circuit failure and limited lifespan caused by dendrite growth, hydrogen evolution and corrosion side reactions of the zinc negative electrode in the actual application process of the current aqueous zinc ion battery, and to provide a preparation method and application of a polypyrrole-derived carbon tube modified zinc negative electrode.

[0005] A method for preparing a polypyrrole-derived carbon tube-modified zinc negative electrode is specifically completed by the following steps:

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

[0007] 2. adding pyrrole monomer and p-toluenesulfonic acid into the methyl orange solution and stirring with a magnetic stirrer to obtain a mixed solution;

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

[0009] 4. transferring the solid reactant II to a tube furnace, raising the temperature to a calcination temperature under an inert gas atmosphere, calcining at the calcination temperature for a period of time, and grinding into particles after calcination to obtain polypyrrole-derived carbon tubes;

[0010] 5. Dispersing the polypyrrole-derived carbon tubes and the binder in a solvent to obtain a slurry; coating the slurry on the surface of the zinc negative electrode, and drying to obtain a polypyrrole-derived carbon tube-modified zinc negative electrode.

[0011] Beneficial effects of the present invention:

[0012] 1. The present invention uses pyrrole as a precursor to prepare carbon tubes; the carbon tubes have abundant defects and a large number of nitrogen-sulfur doped structures; the doped nitrogen and sulfur elements serve as effective zinc-philic sites, which can effectively enrich zinc ions; combined with the hydrophobic properties of carbon materials, the carbon tube material prepared by this method helps to reduce the direct contact between water molecules and the zinc negative electrode, thereby inhibiting hydrogen evolution and corrosion side reactions;

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

[0014] 3. The Zn / / Zn symmetric battery assembled with polypyrrole-derived carbon tubes modified anode can be used at 20 mA / cm 2 The battery can be stably cycled for more than 1500 hours at a high current density, far exceeding the life of the symmetrical battery assembled with the original zinc anode.

[0015] 4. The polypyrrole-derived carbon tube-modified zinc negative electrode prepared by the present invention has the advantages of long cycle life and good stability, and the coating preparation process is simple and has industrial prospects.

[0016] The invention can obtain a polypyrrole-derived carbon tube-modified zinc negative electrode, which is used as the negative electrode of an aqueous zinc ion battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 is a scanning electron microscope image of the polypyrrole-derived carbon tube prepared in Example 1;

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

[0019] Figure 3 The symmetrical cell assembled with the unmodified zinc anode and the polypyrrole-derived carbon tube-modified zinc anode prepared in Example 1 was tested at 20 mA / cm 2 、1mAh / cm 2Time voltage graph under test conditions;

[0020] Figure 4 This is a scanning electron microscope image of the polypyrrole-derived carbon tube prepared in Example 2;

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

[0022] Figure 6 The symmetrical battery assembled with the polypyrrole-derived carbon tube modified zinc anode prepared in Example 2 was charged at 20 mA / cm 2 、1mAh / cm 2 Time voltage graph under test conditions;

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

[0024] Figure 8 is a scanning electron microscope image of the polypyrrole-derived carbon tube prepared in Example 4;

[0025] Fig. 9 This is a scanning electron microscope image of the polypyrrole-derived carbon tube prepared in Example 5. DETAILED DESCRIPTION

[0026] Specific implementation method 1: This implementation method is a method for preparing a polypyrrole-derived carbon tube-modified zinc negative electrode, which is specifically completed by the following steps:

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

[0028] 2. adding pyrrole monomer and p-toluenesulfonic acid into the methyl orange solution and stirring with a magnetic stirrer to obtain a mixed solution;

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

[0030] 4. transferring the solid reactant II to a tube furnace, raising the temperature to a calcination temperature under an inert gas atmosphere, calcining at the calcination temperature for a period of time, and grinding into particles after calcination to obtain polypyrrole-derived carbon tubes;

[0031] 5. Dispersing the polypyrrole-derived carbon tubes and the binder in a solvent to obtain a slurry; coating the slurry on the surface of the zinc negative electrode, and drying to obtain a polypyrrole-derived carbon tube-modified zinc negative electrode.

[0032] Specific embodiment 2: This embodiment differs from specific embodiment 1 in that the concentration of the methyl orange solution in step 1 is 15 mmol / L to 30 mmol / L, and the temperature of the water bath heating in step 1 is 60° C. to 80° C. The other steps are the same as those in specific embodiment 1.

[0033] Specific embodiment 3: This embodiment differs from specific embodiment 1 or 2 in that: the volume ratio of the pyrrole monomer to the methyl orange solution in step 2 is (300 μL-400 μL): (80 mL-120 mL); the mass ratio of p-toluenesulfonic acid to the methyl orange solution in step 2 is (120 mg-150 mg): (80 mL-120 mL); the speed of the magnetic stirring in step 2 is 800 r / min-1000 r / min, and the time of the magnetic stirring is 60 min-90 min. The other steps are the same as those in specific embodiment 1 or 2.

[0034] Specific embodiment 4: This embodiment differs from specific embodiments 1 to 3 in that the concentration of the ferric chloride solution in step 3 is 40 mmol / L to 60 mmol / L; the speed of the magnetic stirring in step 3 is 500 r / min to 1000 r / min, and the time of the magnetic stirring is 10 min to 30 min. The other steps are the same as those in specific embodiments 1 to 3.

[0035] Specific embodiment 5: This embodiment differs from specific embodiments 1 to 4 in that: the ice bath condition described in step 3 is achieved by using an ice-water mixture, and the actual temperature is 0°C; the time for magnetic stirring of the ferric chloride solution under the ice bath condition in step 3 is 1h to 2h; the volume ratio of the ferric chloride solution described in step 3 to the methyl orange solution in the mixed solution is (15mL to 25mL): (80mL to 120mL). The other steps are the same as those of specific embodiments 1 to 4.

[0036] Specific embodiment 6: This embodiment differs from specific embodiments 1 to 5 in that: in step 3, the stirring speed under ice water bath conditions is 700 r / min to 900 r / min, and the stirring time is 24h to 36h; in step 3, deionized water is used to wash the solid reactant I until the washing solution is colorless; the drying temperature in step 3 is 70°C to 90°C, and the drying time is 8h to 10h. The other steps are the same as those in specific embodiments 1 to 5.

[0037] Specific embodiment 7: This embodiment differs from specific embodiments 1 to 6 in that: the inert gas in step 4 is nitrogen, argon, helium or a mixture of the above; the heating rate in step 4 is 2°C / min to 10°C / min; the calcination temperature in step 4 is 700°C to 900°C, and the calcination time is 60min to 100min. The other steps are the same as those in specific embodiments 1 to 6.

[0038] Specific embodiment eight: This embodiment differs from specific embodiments one to seven in that: the solvent described in step five is one or a mixture of N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, dichloromethane and ethanol; the binder described in step five is one or a mixture of polyvinylidene fluoride, polyacrylic acid, sodium carboxymethyl cellulose, styrene-butadiene rubber, chitosan and polyurethane; the mass ratio of the polypyrrole-derived carbon tubes to the binder described in step five is (8-9): (1-2); the mass fraction of the polypyrrole-derived carbon tubes in the slurry described in step five is 20% to 50%. The other steps are the same as specific embodiments one to seven.

[0039] Specific embodiment 9: This embodiment differs from specific embodiments 1 to 8 in that the drying temperature in step 5 is 60°C to 80°C; the thickness of the polypyrrole-derived carbon tube in the polypyrrole-derived carbon tube-modified zinc negative electrode in step 5 is 5 μm to 30 μm. The other steps are the same as those in specific embodiments 1 to 8.

[0040] Specific embodiment 10: This embodiment is a polypyrrole-derived carbon tube modified zinc negative electrode used as the negative electrode of an aqueous zinc ion battery.

[0041] The following examples are used to verify the beneficial effects of the present invention:

[0042] Example 1: A method for preparing a polypyrrole-derived carbon tube-modified zinc negative electrode is specifically completed by the following steps:

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

[0044] The concentration of the methyl orange solution described in step 1 is 15 mmol / L;

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

[0046] 3. Add ferric chloride to deionized water, and then stir the mixture for 30 minutes at a magnetic stirring speed of 1000 r / min to obtain a ferric chloride solution; stir the ferric chloride solution for 1 hour at an ice bath condition of 0°C and a magnetic stirring speed of 800 r / min, then drop 20 mL of the ferric chloride solution into the mixed solution obtained in step 2, and continue to stir the mixture for 24 hours at a magnetic stirring speed of 800 r / min and an ice bath condition to obtain a solid reactant I; wash the solid reactant I three times with deionized water, and then dry it at 70°C for 10 hours to obtain a solid reactant II;

[0047] The concentration of the ferric chloride solution described in step 3 is 50mmol / L;

[0048] Fourth, the solid reactant II is transferred to a tube furnace, heated to 800°C in a nitrogen atmosphere, calcined at 800°C for 80 minutes, and ground into particles after calcination to obtain polypyrrole-derived carbon tubes;

[0049] The heating rate in step 4 is 5°C / min;

[0050] 5. Disperse 45 mg of polypyrrole-derived carbon tubes and polyvinylidene fluoride in 140 μL of N-methylpyrrolidone to obtain a slurry; apply the slurry to the surface of the zinc negative electrode with a thickness of 100 μm after removing the oxide layer, adjust the coating thickness of the coater to 300 μm, and dry at 80° C. for 12 h to obtain a polypyrrole-derived carbon tube-modified zinc negative electrode;

[0051] The mass ratio of the polypyrrole-derived carbon tubes to polyvinylidene fluoride in step 5 is 9:1;

[0052] In step 5, the zinc negative electrode with a thickness of 100 μm after removing the oxide layer is polished with sandpaper until it is bright to remove the oxide layer, thereby obtaining the zinc negative electrode with a thickness of 100 μm after removing the oxide layer.

[0053] Figure 1 is a scanning electron microscope image of the polypyrrole-derived carbon tube prepared in Example 1;

[0054] from Figure 1 It can be seen that the polypyrrole-derived carbon tubes prepared in Example 1 have an obvious tubular structure.

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

[0056] from Figure 2 It can be seen that the polypyrrole-derived carbon tubes prepared in Example 1 have obvious sulfur doping signals.

[0057] The symmetrical battery assembled with polypyrrole-derived carbon tube-modified zinc negative electrode was prepared by using Example 1, which was specifically completed by the following steps:

[0058] ①, punching the polypyrrole-derived carbon tube-modified zinc anode prepared in Example 1 into a disc with a diameter of 14 mm using a punching machine, as an electrode plate of a symmetrical battery;

[0059] ② Use a punching machine to punch the glass fiber into discs with a diameter of 16 mm as a diaphragm;

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

[0061] ④. Place the battery pole piece and diaphragm in the button battery negative electrode shell in order, add 70 microliters of electrolyte to wet the diaphragm, then add the other side electrode piece, stainless steel gasket, spring and button battery positive electrode shell, and then use a sealing machine at 50kg / cm 2 Button symmetrical battery encapsulated under pressure.

[0062] Figure 3 The symmetrical cell assembled with the unmodified zinc anode and the polypyrrole-derived carbon tube-modified zinc anode prepared in Example 1 was tested at 20 mA / cm 2 、1mAh / cm 2 Time voltage graph under test conditions;

[0063] from Figure 3 It can be seen that compared with the symmetrical battery composed of untreated pure zinc sheets, the cycle life of the symmetrical battery composed of the polypyrrole-derived carbon tube-modified zinc negative electrode prepared in Example 1 is significantly improved, with a stable cycle of more than 1500 hours. During the entire cycle, there is no obvious fluctuation in the polarization voltage, which strongly proves the cycle stability of the modified zinc negative electrode.

[0064] Example 2: This example is different from Example 1 in that in step 2, 350 μL of pyrrole monomer is added to 100 mL of methyl orange solution, and magnetic stirring is performed at a speed of 800 r / min for 60 min to obtain a mixed solution. Other steps and parameters are the same as those in Example 1.

[0065] Figure 4 This is a scanning electron microscope image of the polypyrrole-derived carbon tube prepared in Example 2;

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

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

[0068] from Figure 5 It can be seen that no sulfur doping signal can be detected in the polypyrrole-derived carbon tubes prepared in Example 2 without p-toluenesulfonic acid, which proves that p-toluenesulfonic acid is indispensable for sulfur doping in the preparation process of carbon tubes.

[0069] The symmetrical battery assembled with polypyrrole-derived carbon tube-modified zinc negative electrode was prepared by using Example 2, which was specifically completed by the following steps:

[0070] ①, punching the zinc negative electrode with carbon tube coating on the surface prepared in Example 2 into a disc with a diameter of 14 mm by a punching machine, as an electrode plate of a symmetrical battery;

[0071] ② Use a punching machine to punch the glass fiber into discs with a diameter of 16 mm as a diaphragm;

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

[0073] ④. Place the battery pole piece and diaphragm in the button battery negative electrode shell in order, add 70 microliters of electrolyte to wet the diaphragm, then add the other side electrode piece, stainless steel gasket, spring and button battery positive electrode shell, and then use a sealing machine at 50kg / cm 2 Button symmetrical battery encapsulated under pressure.

[0074] Figure 6 The symmetrical battery assembled with the polypyrrole-derived carbon tube modified zinc anode prepared in Example 2 was charged at 20 mA / cm 2 、1mAh / cm 2 Time voltage graph under test conditions;

[0075] from Figure 6 It can be seen that the cycle life of the symmetrical battery composed of the polypyrrole-derived carbon tube-modified zinc anode synthesized without p-toluenesulfonic acid is less than 1200h, which is better than the bare zinc electrode under the same conditions but inferior to the symmetrical battery composed of the carbon tube-modified zinc anode synthesized with the participation of p-toluenesulfonic acid, proving the important role of p-toluenesulfonic acid on the carbon tube-modified zinc anode.

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

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

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

[0079] Example 4: This example is different from Example 2 in that the concentration of the methyl orange solution in step 1 is 10 mmol / L. Other steps and parameters are the same as those in Example 2.

[0080] Figure 8 is a scanning electron microscope image of the polypyrrole-derived carbon tube prepared in Example 4;

[0081] from Figure 8 It can be seen that when the methyl orange concentration is low, the prepared polypyrrole-derived carbon nanotubes have more spherical impurities.

[0082] Example 5: This example is different from Example 2 in that the concentration of the methyl orange solution in step 1 is 40 mmol / L. Other steps and parameters are the same as those in Example 2.

[0083] Fig. 9 is a scanning electron microscope image of the polypyrrole-derived carbon tube prepared in Example 5;

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

Claims

1. A method for preparing a polypyrrole-derived carbon tube-modified zinc negative electrode, characterized in that The preparation method is specifically completed according to the following steps:

1. Add methyl orange to deionized water, and then stir in a water bath until the methyl orange is completely dissolved to obtain a methyl orange solution; 2. adding pyrrole monomer and p-toluenesulfonic acid into the methyl orange solution and stirring with a magnetic stirrer to obtain a mixed solution; 3. Add ferric chloride to deionized water and stir magnetically to obtain a ferric chloride solution; The ferric chloride solution is magnetically stirred for a period of time in an ice bath, and then added dropwise to the mixed solution, and stirred for a period of time in an ice water bath to obtain a solid reactant I; The solid reactant I is washed and dried to obtain a solid reactant II; 4. transferring the solid reactant II to a tube furnace, raising the temperature to a calcination temperature under an inert gas atmosphere, calcining at the calcination temperature for a period of time, and grinding into particles after calcination to obtain polypyrrole-derived carbon tubes; 5. Dispersing the polypyrrole-derived carbon tubes and the binder in a solvent to obtain a slurry; coating the slurry on the surface of the zinc negative electrode, and drying to obtain a polypyrrole-derived carbon tube-modified zinc negative electrode.

2. The method for preparing a polypyrrole-derived carbon tube-modified zinc negative electrode according to claim 1, characterized in that The concentration of the methyl orange solution in step 1 is 15 mmol / L to 30 mmol / L; the temperature of the water bath heating in step 1 is 60° C. to 80° C.

3. The method for preparing a polypyrrole-derived carbon tube-modified zinc negative electrode according to claim 1, characterized in that The volume ratio of the pyrrole monomer described in step 2 to the methyl orange solution is (300 μL to 400 μL): (80 mL to 120 mL); the volume ratio of the mass of p-toluenesulfonic acid described in step 2 to the methyl orange solution is (120 mg to 150 mg): (80 mL to 120 mL); the speed of the magnetic stirring described in step 2 is 800 r / min to 1000 r / min, and the time of the magnetic stirring is 60 min to 90 min.

4. The method for preparing a polypyrrole-derived carbon tube-modified zinc negative electrode according to claim 1, characterized in that The concentration of the ferric chloride solution in step 3 is 40 mmol / L to 60 mmol / L; the speed of the magnetic stirring in step 3 is 500 r / min to 1000 r / min, and the time of the magnetic stirring is 10 min to 30 min.

5. The method for preparing a polypyrrole-derived carbon tube-modified zinc negative electrode according to claim 1, characterized in that The ice bath condition described in step 3 is achieved by using an ice-water mixture, and the actual temperature is 0° C.; the time for magnetically stirring the ferric chloride solution under the ice bath condition in step 3 is 1 h to 2 h; the volume ratio of the ferric chloride solution described in step 3 to the methyl orange solution in the mixed solution is (15 mL to 25 mL): (80 mL to 120 mL).

6. The method for preparing a polypyrrole-derived carbon tube-modified zinc negative electrode according to claim 1, characterized in that In step 3, the stirring speed is continuously 700 r / min to 900 r / min under ice water bath conditions, and the stirring time is continuously 24 h to 36 h. In step 3, the solid reactant I is washed with deionized water until the washing solution is colorless. The drying temperature described in step 3 is 70°C to 90°C, and the drying time is 8 h to 10 h.

7. The method for preparing a polypyrrole-derived carbon tube-modified zinc negative electrode according to claim 1, characterized in that The inert gas described in step 4 is nitrogen, argon, helium or a mixture of the above; the heating rate described in step 4 is 2°C / min to 10°C / min; the calcination temperature described in step 4 is 700°C to 900°C, and the calcination time is 60min to 100min.

8. The method for preparing a polypyrrole-derived carbon tube-modified zinc negative electrode according to claim 1, characterized in that The solvent described in step 5 is one or a mixture of several of N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, dichloromethane and ethanol; the binder described in step 5 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-derived carbon tubes to the binder described in step 5 is (8-9):(1-2); the mass fraction of the polypyrrole-derived carbon tubes in the slurry described in step 5 is 20% to 50%.

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

10. Use of a polypyrrole-derived carbon tube modified zinc negative electrode prepared by the preparation method according to claim 1, characterized in that A polypyrrole-derived carbon tube-modified zinc negative electrode is used as the negative electrode of an aqueous zinc ion battery.

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