Preparation Method and Application of Zinc Powder Anode Material Coated with Titanium Dioxide Nanoparticles

Abstract

The present invention discloses a preparation method of a titanium dioxide nanoparticle-coated zinc powder negative electrode material, which comprises the following steps: S1: After dissolving a titanate coupling agent in a solvent, gradually add a phosphate surfactant and absolute ethanol to obtain a mixed solution A; S2: Add zinc powder to obtain a mixed solution B containing zinc powder; S3: Under the stirring state, control the reaction temperature to be 45°C to 65°C, slowly drop ascorbic acid into the mixed solution B, and continue stirring and reacting to obtain a mixed solution C; S4: Filter the mixed solution C and then put it into a vacuum oven for drying to obtain the titanium dioxide nanoparticle-coated zinc powder negative electrode material. The zinc powder negative electrode material prepared by the present invention can effectively inhibit the self-corrosion and passivation of zinc powder, reduce the gas evolution amount inside the battery, improve the utilization rate of zinc powder, increase the battery capacity, extend the storage time of the battery and enhance the safety performance of the battery.

Description

Technical Field

[0001] The invention relates to the technical field of alkaline zinc-manganese batteries, and in particular to a preparation method and application of a titanium dioxide nanoparticle-coated zinc powder negative electrode material. Background Art

[0002] In recent years, the alkaline zinc-manganese battery industry has developed rapidly and quickly spread to various fields of people's daily life, gradually replacing ordinary zinc-manganese batteries and becoming the mainstream of the market. With the development of society, people have put forward higher requirements for the performance of alkaline zinc-manganese batteries. As an important component of alkaline zinc-manganese batteries, negative electrode materials play an important role in the overall performance of batteries. Metallic zinc has become an important component of negative electrode materials for alkaline zinc-manganese batteries due to its high activity, abundant sources, low toxicity and low price.

[0003] However, due to its high activity, it is very easy to corrode in alkaline solution, causing battery self-discharge, accompanied by the generation of hydrogen. When the gas precipitated reaches a certain level, the battery expands, causing electrolyte leakage, shortening the storage time of the battery; when the alkaline zinc-manganese battery is discharged, as zinc dissolves, a dense Zn0 film is formed on the electrode surface, which hinders the migration of KOH electrolyte, thereby reducing the actual surface area of the zinc electrode and causing electrode passivation. As a result, the utilization rate of active materials is reduced, the battery capacity is reduced, and the battery life is shortened. How to reduce the gassing and passivation of zinc negative electrode materials and improve the electrochemical performance of alkaline zinc-manganese batteries has become an important issue that plagues the development of the industry. Summary of the invention

[0004] In view of the above shortcomings of the prior art, the present invention provides a method for preparing a zinc powder negative electrode material coated with titanium dioxide nanoparticles to solve the problems that the existing zinc powder negative electrode material is easily corroded in alkaline solution, resulting in gas evolution, and the surface passivation of the zinc powder negative electrode material during discharge.

[0005] In order to achieve the above purpose, the technical solution adopted by the present invention is:

[0006] A method for preparing a titanium dioxide nanoparticle-coated zinc powder negative electrode material, the preparation method comprising the following steps:

[0007] S1: After dissolving the titanate coupling agent in a solvent, gradually adding a phosphate surfactant and anhydrous ethanol to obtain a mixed solution A;

[0008] S2: adding zinc powder to the mixed solution A to obtain a mixed solution B containing zinc powder;

[0009] S3: Under stirring, control the reaction temperature to 45°C to 65°C, slowly drip ascorbic acid into the mixed solution B, continue stirring the reaction for 1 to 2 hours, and obtain a mixed solution C;

[0010] S4: After filtering the mixed solution C, it is placed in a vacuum oven for drying to obtain the zinc powder negative electrode material coated with titanium dioxide nanoparticles.

[0011] Nano-titanium dioxide has attracted much attention due to its advantages such as certain conductivity, stable chemical properties, and no secondary pollution. In this application, the in-situ growth reaction of reducing titanate coupling agents by ascorbic acid on the surface of zinc powder enables the uniform coating of titanium dioxide nanoparticles on the surface of the zinc powder negative electrode material. The zinc powder prepared by this method has a uniform and loose layer of titanium dioxide nanoparticles on its surface. During the electrochemical reaction process, this loose nanoparticle structure, on the one hand, can disrupt the ordered and dense packing of the ZnO film to form a porous and loose ZnO film, maintaining a certain channel for the migration of OH - ions, greatly improving the utilization rate of zinc powder; on the other hand, the titanium dioxide nanoparticles have a certain conductivity, avoiding direct contact between the electrolyte and the zinc surface, while maintaining the electrochemical reaction of the battery, improving the self-discharge performance of the battery, and having a certain effect on inhibiting gas evolution in the battery.

[0012] Preferably, the titanate coupling agent is at least one of tetrabutyl titanate, monoalkoxy titanate, triisostearoyl titanate isopropyl ester, isopropyl tri(dioctylphosphate acyloxy) titanate, and isopropyl dioleate acyloxy (dioctylphosphate acyloxy) titanate. These titanate coupling agents can be chemically coupled with trace carboxyl groups or hydroxyl groups adsorbed on the surface of the zinc negative electrode material through their alkoxy groups, so a tight and uniform titanium-containing organic coating layer can be formed on the surface of the zinc powder negative electrode material through chemical bonds.

[0013] Preferably, the phosphate salt is at least one of polyoxyethylene dodecyl ether phosphate salt, perfluoroalkyl ethanol phosphate DEA salt, polyoxyethylene alkyl phenyl ether phosphate triethanolamine salt, fatty alcohol polyoxyethylene ether phosphate salt, and perfluoroalkyl ethanol polyoxyethylene ether phosphate amine salt. The phosphate salt surfactant contains both hydrophilic and hydrophobic functional groups, shows strong adsorption performance on the surface of the zinc powder negative electrode material, and has a repulsive performance towards the solution, causing the active aqueous solution to undergo solid-liquid separation from the zinc powder, avoiding direct contact between the solution and the zinc powder, and suppressing hydrogen evolution. The phosphate salt surfactant has an agglomeration property when mixed with a titanate coupling agent. During the solid-liquid mixing process, these phosphate salt surfactants agglomerate with the titanate coupling agent and adsorb on the surface of the metal powder material to form a tightly adhering titanium-containing organic layer. Further reduction can form a uniform and complete titanium dioxide nanoparticle coating layer on the surface of the zinc powder material; and the titanium dioxide chemically bonds with the surface of the zinc negative electrode material and is generated in-situ, having a stable interface structure. By controlling the ratio of the titanate coupling agent to the phosphate salt surfactant, the content of the titanate coupling agent adsorbed on the zinc powder surface can be adjusted, and finally, the coating amount of titanium dioxide nanoparticles on the zinc powder surface can be adjusted through reduction. More preferably, the phosphate salt is perfluoroalkyl ethanol phosphate DEA salt or perfluoroalkyl ethanol polyoxyethylene ether phosphate amine salt. The addition of the perfluoro phosphate salt in this application further ensures the uniform coating of titanium dioxide nanoparticles. At the same time, the perfluoro phosphate salt in this application can also effectively prevent the electrolyte from corroding the zinc powder and inhibit the occurrence of hydrogen evolution reactions.

[0014] Preferably, the solvent is at least one of solvent oil, petroleum ether, benzene alcohol, and isopropyl alcohol. The preferred solvent has good solubility for the titanate coupling agent and is easy to remove, which can improve the uniformity of the coating of the titanate coupling agent on the surface of the zinc powder negative electrode material, thereby obtaining a more uniform titanium dioxide coating layer.

[0015] Preferably, the mass ratio of the titanate coupling agent, solvent, phosphate salt surfactant to absolute ethanol is 2:50:1 - 3:30. By strictly controlling the mass ratio of the titanate coupling agent to the phosphate salt surfactant in the mixed solution A, the content of titanium dioxide nanoparticles attached to the zinc powder surface can be adjusted.

[0016] Preferably, the mass ratio of the mixed solution A to the zinc powder is 1:1.

[0017] Preferably, the mass ratio of ascorbic acid to zinc powder is 1:25 - 40.

[0018] Preferably, the drying temperature of the vacuum oven is controlled at 80°C - 120°C, and the drying time is 12 - 24 h.

[0019] Another aspect of the present application is to provide an application of the preparation method of the zinc powder negative electrode material coated with titanium dioxide nanoparticles as described above. The prepared zinc powder negative electrode material is compounded with a KOH electrolyte solution and a polyacrylic acid binder to obtain a paste-like zinc paste; the zinc paste is filled into an LR6 nickel-plated steel shell with a separator paper and a manganese ring, and then a copper nail of the negative electrode current collector is inserted into the zinc paste; finally, the battery is sealed and formed to assemble a complete LR6 alkaline zinc-manganese battery.

[0020] Advantages of the present invention:

[0021] The titanium dioxide nanoparticle-coated zinc powder negative electrode material prepared by the present invention has a complete and uniform nanoparticle coating layer and a stable interfacial structure, a long storage time, and its surface structure is not easily damaged.

[0022] The titanium dioxide nanoparticle-coated zinc powder negative electrode material prepared by the present invention can effectively inhibit the self-corrosion of zinc powder, reduce the gas evolution amount inside the battery, extend the service life of the battery, and improve the safety performance of the battery.

[0023] The titanium dioxide nanoparticle-coated zinc powder negative electrode material prepared by the present invention can effectively inhibit the passivation of zinc powder, improve the utilization rate of zinc powder, increase the battery capacity, and extend the service life of the battery.

[0024] The preparation process of the titanium dioxide nanoparticle-coated zinc powder negative electrode material provided by the present invention is simple and effective, has strong controllability, low production cost, and can be mass-produced. Description of the drawings

[0025] Figure 1 It is a process flow chart of the production of the zinc powder negative electrode material of the present invention;

[0026] Figure 2 (a) is an SEM image of untreated zinc powder, Figure 2 (b) is an SEM image of the zinc powder produced in Example 1, Figure 2 (c) is an SEM image of the zinc powder produced in Example 2, Figure 2 (d) is an SEM image of the zinc powder produced in Example 3;

[0027] Figure 3 It is a comparison chart of the discharge curves of the alkaline zinc-manganese batteries of Examples 1, 2, and 3 and the control battery under a constant current discharge condition of 100 mA;

[0028] Figure 4 It is a comparison chart of the discharge curves of the alkaline zinc-manganese batteries of Examples 1, 2, and 3 and the control battery under a constant current discharge condition of 250 mA;

[0029] Figure 5Discharge curve comparison diagram of the alkaline zinc-manganese batteries of Examples 1, 2, and 3 and the control battery under the variable working conditions of 1.5W / 650mW discharge. Detailed implementation manners

[0030] The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments in the following description are only examples, and those skilled in the art can think of other obvious variations.

[0031] Example 1

[0032] The preparation method of the zinc powder negative electrode material coated with titanium dioxide nanoparticles in this example is as Figure 1 shown. The preparation method includes the following steps: S1: Dissolve 2 g of commercial tetrabutyl titanate in 50 g of petroleum ether, and obtain a clear solution after 1 h of magnetic stirring; Add 2 g of polyoxyethylene dodecyl ether phosphate salt to 30 g of absolute ethanol, and after 2 h of stirring, then mix the two solutions and perform ultrasonic treatment for 1 h to obtain a mixed solution A; S2: Add 84 g of zinc powder to the mixed solution A to obtain a mixed solution B containing zinc powder; S3: Under continuous stirring of a strong stirrer, dropwise add 3 g of ascorbic acid, control the reaction temperature at 45 °C, continue stirring for 2 h and then filter to obtain a mixed solution C; S4: Place the zinc powder after filtering the mixed solution C in a vacuum oven at 100 °C and dry it for 18 h to obtain the zinc powder negative electrode material coated with titanium dioxide nanoparticles. It can be seen from Figure 2 (a) that the surface of the untreated zinc powder is very smooth. It can be seen from Figure 2 (b) that the surface of the zinc powder treated by the present invention is coated with a layer of uniform and dense nanoparticles, and the thickness of the nanoparticles is about 80 nm. The zinc powder prepared by this experimental method is denoted as B.

[0033] Mix the obtained zinc powder negative electrode material coated with titanium dioxide nanoparticles, a KOH electrolyte solution with a mass concentration of 32%, and a polyacrylic acid binder in a mass ratio of 300:135:1.5, and stir until a uniform paste-like zinc paste is obtained. Take 20 g of the zinc paste and put it into a gas analysis bottle, then fill the gas analysis bottle with liquid paraffin, and place it in a 60 °C constant temperature oil bath box filled with paraffin oil. Record the scale value of the liquid concave surface in the gas analysis bottle at a fixed time every day for a total of 5 days; Take the uncoated zinc powder and perform a gas evolution experiment in the same way as a control group; Denote the zinc powder in the control group as A. The comparison data of the total gas evolution volume (ml) of the zinc paste is shown in Table 1:

[0034] Table 1

[0035] Day 1 Day 2 Day 3 Day 4 Day 5 A 0.05 0.12 0.2 0.26 0.35 B 0 0.03 0.08 0.12 0.16

[0036] As can be seen from Table 1, the total gas evolution volume of the zinc paste in Experiment 5 of this Example B is 0.16 ml, and the gas evolution volume of the control group A is 0.35 ml. The total gas evolution volume of the zinc paste made from the zinc powder of the present invention after 5 days is reduced by 0.19 ml.

[0037] Take 6.5 g of zinc paste and put it into an LR6 nickel-plated steel shell with a separator paper and a manganese ring. Then insert the copper nail of the negative current collector into the zinc paste. Finally, seal the battery to form a complete LR6 alkaline zinc-manganese battery. The new battery assembled with the zinc powder prepared in this experiment and the alkaline zinc-manganese battery (control battery) made of untreated zinc powder are subjected to constant-temperature discharge detection and comparison in a constant-temperature and humidity chamber (20 ± 1 °C, RH 35 - 75%). Detection instrument: Wuhan Blue Electric Battery Test System (CT3002A), and small current (100 mA), medium current (250 mA) and variable working condition (1.5 W / 650 mW) discharge tests are carried out respectively.

[0038] Discharge mode:

[0039] Small current discharge: 100 mA, continuous discharge for 24 h / day; until the cut-off voltage is 0.8 V.

[0040] Medium current discharge: 250 mA, continuous discharge for 24 h / day; until the cut-off voltage is 0.8 V.

[0041] Variable working condition discharge: discharge at 1.5 W for 2 s, then discharge at 650 mW for 28 s, repeat 10 times and then stop for 55 min; repeat until the cut-off voltage is 1.05 V.

[0042] From Figure 3 、 4 、5, it can be known that the discharge conditions of the LR6 alkaline zinc-manganese battery made by loading titanium dioxide nanoparticles on the surface of zinc powder as the negative electrode material in this experiment are 25.51 h, 8.78 h and 150 times respectively under small current, medium current and variable working condition discharge conditions, and the discharge conditions of the control battery are 21.72 h, 7.34 h and 126 times respectively. Compared with the control battery, the discharge performance is improved by 3.79 h, 1.44 h and 24 times respectively.

[0043] Example 2

[0044] The preparation method of the titanium dioxide nanoparticle-coated zinc powder anode material of this embodiment, the preparation method includes the following steps: S1: Dissolve 2 g of commercial tetrabutyl titanate in 50 g of petroleum ether, and obtain a clear solution after 1 h of magnetic stirring; Add 1 g of polyoxyethylene dodecyl ether phosphate salt to 30 g of absolute ethanol, after 2 h of stirring, then mix the two solutions and perform ultrasonic treatment for 1 h to obtain a mixed solution A; S2: Add 83 g of zinc powder to the mixed solution A to obtain a mixed solution B containing zinc powder; S3: Under continuous stirring of a strong stirrer, dropwise add 3 g of ascorbic acid, control the reaction temperature at 45 °C, continue stirring for 2 h and then filter to obtain a mixed solution C; S4: Place the zinc powder after filtering the mixed solution C in a vacuum oven at 100 °C and dry it for 18 h to obtain the titanium dioxide nanoparticle-coated zinc powder anode material. From Figure 2 As can be seen from (c), the nanoparticle coating layer on the surface of the zinc powder after being treated by the present invention is relatively thin, and the thickness of the nanoparticles is about 40 nm. The zinc powder prepared by this experimental method is denoted as C.

[0045] Mix the obtained titanium dioxide nanoparticle-coated zinc powder anode material, a KOH electrolyte solution with a mass concentration of 32%, and a polyacrylic acid binder according to a mass ratio of 300:135:1.5, and stir until a uniform paste-like zinc paste is obtained. Take 20 g of the zinc paste and put it into a gas evolution bottle, then fill the gas evolution bottle with liquid paraffin, place it in a 60 °C constant temperature oil bath box filled with paraffin oil, record the scale value of the liquid concave surface in the gas evolution bottle at a fixed time every day, and record for a total of 5 days; Take the uncoated zinc powder and conduct a gas evolution experiment in the same way as a control group, and the zinc powder in the control group is denoted as A. The data comparison of the total gas evolution volume (ml) of the zinc paste is shown in Table 2:

[0046] Table 2

[0047] Day 1 Day 2 Day 3 Day 4 Day 5 A 0.05 0.12 0.2 0.26 0.35 C 0 0.05 0.11 0.18 0.26

[0048] As can be seen from Table 2, the total gas evolution volume of the zinc paste after 5 days of Experiment C in this embodiment is 0.26 ml, and the gas evolution volume of the control group A is 0.35 ml. The total gas evolution volume of the zinc paste made of the zinc powder of the present invention after 5 days is reduced by 0.09 ml.

[0049] Take 6.5 g of the zinc paste and put it into an LR6 nickel-plated steel shell equipped with a separator paper and a manganese ring, then insert the copper nail of the negative electrode current collector into the zinc paste, and finally seal the battery to form a complete LR6 alkaline zinc-manganese battery. From Figure 3 、 4As can be seen from FIGS. 5, in this experiment, an LR6 alkaline zinc-manganese battery made with titanium dioxide nanoparticles loaded on the surface of zinc powder as the negative electrode material had discharge times of 24.05 h, 8.2 h, and 139 times under low-current, medium-current, and variable operating conditions, respectively. The discharge times of the control battery were 21.72 h, 7.34 h, and 126 times, respectively. Compared with the control battery, the discharge performance increased by 2.33 h, 0.86 h, and 13 times, respectively.

[0050] Example 3

[0051] The preparation method of the titanium dioxide nanoparticle-coated zinc powder negative electrode material in this example includes the following steps: S1: Dissolve 2 g of commercial tetrabutyl titanate in 50 g of petroleum ether, and obtain a clear solution after 1 h of magnetic stirring; add 3 g of polyoxyethylene dodecyl ether phosphate salt to 30 g of absolute ethanol, and after 2 h of stirring, mix the two solutions and perform ultrasonic treatment for 1 h to obtain a mixed solution A; S2: Add 85 g of zinc powder to the mixed solution A to obtain a mixed solution B containing zinc powder; S3: While continuously stirring with a strong stirrer, dropwise add 3 g of ascorbic acid, control the reaction temperature at 45 °C, continue stirring for 2 h, and then filter to obtain a mixed solution C; S4: Place the zinc powder after filtering the mixed solution C in a vacuum oven at 100 °C and dry it for 18 h to obtain the titanium dioxide nanoparticle-coated zinc powder negative electrode material. Figure 2 As can be seen from FIG. 8(d), a relatively thick layer of nanoparticles covers the surface of the zinc powder after treatment according to the present invention, and the thickness of the nanoparticles is about 120 nm. The zinc powder prepared by this experimental method is denoted as D.

[0052] Mix the obtained titanium dioxide nanoparticle-coated zinc powder negative electrode material, a KOH electrolyte solution with a mass concentration of 32%, and a polyacrylic acid binder in a mass ratio of 300:135:1.5, and stir until a uniform paste-like zinc paste is obtained. Take 20 g of the zinc paste and put it into a gas analysis bottle, then fill the gas analysis bottle with liquid paraffin, place it in a 60 °C constant temperature oil bath box filled with paraffin oil, and record the scale value of the liquid concave surface in the gas analysis bottle at a fixed time every day for a total of 5 days; take the uncoated zinc powder and perform a gas evolution experiment in the same manner as a control group, and the zinc powder in the control group is denoted as A. The data comparison of the total gas evolution volume (ml) of the zinc paste is shown in Table 3:

[0053] Table 3

[0054]

[0055]

[0056] As can be seen from Table 3, the total gas evolution volume of the zinc paste after 5 days in Experiment D was 0.12 ml, and the gas evolution volume of the control group A was 0.35 ml. The total gas evolution volume of the zinc paste made from the zinc powder of the present invention decreased by 0.23 ml after 5 days.

[0057] 6.5 g of zinc paste is placed into a nickel-plated steel LR6 case equipped with a separator paper and a manganese ring. Then, the copper nail of the negative current collector is inserted into the zinc paste. Finally, the battery is sealed and formed to assemble a complete LR6 alkaline zinc-manganese battery. From Figure 3 , 4 , and 5, it can be seen that for the LR6 alkaline zinc-manganese battery made with titanium dioxide nanoparticles loaded on the surface of zinc powder as the negative electrode material in this experiment, the discharge durations under low current, medium current, and variable working condition discharge are 22.61 h, 7.66 h, and 129 times respectively, while those of the control battery are 21.72 h, 7.34 h, and 126 times respectively. Compared with the control battery, the discharge performances are improved by 0.89 h, 0.32 h, and 3 times respectively.

[0058] Example 4

[0059] The preparation method of the negative electrode material of zinc powder coated with titanium dioxide nanoparticles in this example is basically the same as that in Example 1, except that the phosphate salt in this example is DEA salt of perfluoroalkyl ethanol phosphate.

[0060] The total gas evolution volume of the zinc paste made from the zinc powder of the present invention is reduced by 0.25 ml after 5 days. For the LR6 alkaline zinc-manganese battery made with titanium dioxide nanoparticles loaded on the surface of zinc powder as the negative electrode material in this example, the discharge durations under low current, medium current, and variable working condition discharge are 25.74 h, 8.9 h, and 153 times respectively, while those of the control battery are 21.72 h, 7.34 h, and 126 times respectively. Compared with the control battery, the discharge performances are improved by 4.02 h, 1.56 h, and 27 times respectively.

[0061] Example 5

[0062] The preparation method of the negative electrode material of zinc powder coated with titanium dioxide nanoparticles in this example is basically the same as that in Example 1, except that the phosphate salt in this example is amine salt of perfluoroalkyl ethanol polyoxyethylene ether phosphate.

[0063] The total gas evolution volume of the zinc paste made from the zinc powder of the present invention is reduced by 0.26 ml after 5 days. For the LR6 alkaline zinc-manganese battery made with titanium dioxide nanoparticles loaded on the surface of zinc powder as the negative electrode material in this example, the discharge durations under low current, medium current, and variable working condition discharge are 25.81 h, 8.95 h, and 155 times respectively, while those of the control battery are 21.72 h, 7.34 h, and 126 times respectively. Compared with the control battery, the discharge performances are improved by 4.09 h, 1.61 h, and 29 times respectively.

[0064] The basic principles, main features and advantages of the present invention have been shown and described above. Those skilled in the art should understand that the present invention is not limited by the above embodiments, and what is described in the above embodiments and the specification is only the principle of the present invention. Without departing from the spirit and scope of the present invention, various changes and improvements will occur to the present invention, and these changes and improvements all fall within the scope of the present invention claimed.

Claims

1. A preparation method of a zinc powder negative electrode material coated with titanium dioxide nanoparticles, characterized in that, The preparation method comprises the following steps: S1: After dissolving a titanate coupling agent in a solvent, gradually add a phosphate ester salt surfactant and absolute ethanol to obtain a mixed solution A; S2: Add zinc powder to the mixed solution A to obtain a mixed solution B containing zinc powder; S3: Under a stirring state, control the reaction temperature at 45°C to 65°C, slowly drop ascorbic acid into the mixed solution B, and continue stirring and reacting for 1 to 2 h to obtain a mixed solution C; S4: Filter the mixed solution C and then put it into a vacuum oven for drying to obtain the zinc powder negative electrode material coated with titanium dioxide nanoparticles; The titanate coupling agent is at least one of butyl titanate, monoalkoxy titanate, isopropyl tri(isostearoyl) titanate, isopropyl tri(dioctylphosphate acyloxy) titanate, isopropyl dioleoyl acyloxy (dioctylphosphate acyloxy) titanate; the phosphate ester salt is at least one of polyoxyethylene dodecyl ether phosphate salt, perfluoroalkyl ethanol phosphate DEA salt, polyoxyethylene alkyl phenyl ether phosphate triethanolamine salt, fatty alcohol polyoxyethylene ether phosphate salt, perfluoroalkyl ethanol polyoxyethylene ether phosphate amine salt.

2. The preparation method of the zinc powder negative electrode material coated with titanium dioxide nanoparticles according to claim 1, characterized in that, The phosphate ester salt is perfluoroalkyl ethanol phosphate DEA salt or perfluoroalkyl ethanol polyoxyethylene ether phosphate amine salt.

3. The preparation method of the titanium dioxide nanoparticle-coated zinc powder anode material according to claim 1, characterized in that, The solvent is at least one of solvent oil, petroleum ether, benzyl alcohol, and isopropyl alcohol.

4. The preparation method of the titanium dioxide nanoparticle-coated zinc powder negative electrode material according to claim 1, characterized in that, The mass ratio of the titanate coupling agent, solvent, phosphate ester salt surfactant, and absolute ethanol is 2:50:1 to 3:

30.

5. The preparation method of the titanium dioxide nanoparticle-coated zinc powder anode material according to claim 1, characterized in that, The mass ratio of the mixed solution A to zinc powder is 1:

1.

6. The preparation method of the zinc powder negative electrode material coated with titanium dioxide nanoparticles according to claim 1, characterized in that, The mass ratio of ascorbic acid to zinc powder is 1:25 to 40.

7. The preparation method of the titanium dioxide nanoparticle-coated zinc powder anode material according to claim 1, characterized in that, The drying temperature of the vacuum oven is controlled at 80°C to 120°C, and the drying time is 12 to 24 h.

8. Use of the method for preparing the titanium dioxide nanoparticle-coated zinc powder negative electrode material according to any one of claims 1 to 7, characterized in that, Mix the prepared zinc powder negative electrode material with a KOH electrolyte solution and a polyacrylic acid binder to obtain a paste-like zinc paste; put the zinc paste into a nickel-plated steel shell with a separator paper and a manganese ring, and then insert the copper nail of the negative electrode current collector into the zinc paste; finally, seal and form the battery to assemble a complete alkaline zinc-manganese battery.

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