CN114314670A - Modification method of copper ion implanted zinc battery anode material delta-manganese dioxide - Google Patents

Abstract

A method for modifying δ-manganese dioxide, a positive electrode material of a zinc battery by implanting copper ions, relates to a method for preparing a positive electrode material for the battery. The purpose of the present invention is to solve the problems that traditional lithium ion batteries are toxic, flammable, require anhydrous operating environment and consume large lithium resources. Methods: 1. Preparation of δ-manganese dioxide powder; 2. Preparation of viscous electrode slurry; 3. Copper ion implantation. The performance of the aqueous zinc ion battery assembled by the copper ion-implanted δ-manganese dioxide electrode sheet prepared by the present invention is compared with the performance of the aqueous zinc ion battery assembled with the electrode sheet loaded with δ-manganese dioxide without copper ion implantation. It has a high specific capacity of 519.4mAhg ^-1 at 0.1Ag ^-1 , while the aqueous zinc-ion battery assembled with the electrode sheet loaded with δ-manganese dioxide has a capacity of only 209.7mAhg ^-1 at the same current density.

Description

A method for modifying δ-manganese dioxide, a positive electrode material of zinc battery implanted with copper ions

technical field

The invention relates to a preparation method of a battery positive electrode material.

Background technique

Energy and the environment are two major issues that must be dealt with for human survival and social development. With the rapid development of science and technology, energy is rapidly consumed, but fossil energy such as coal and oil is not inexhaustible. At the same time, climate And the environment is also deteriorating day by day, which is contrary to the green and healthy life pursued by human beings, so the development of renewable energy such as solar energy and wind energy has become a global trend. However, these renewable natural energy cannot be widely used in daily life due to uncontrollable factors such as weather and geography. Therefore, the application of energy storage devices is crucial to overcome these challenges. Although the widely used lithium-ion batteries have many advantages, they are not only toxic and flammable, but also require a water-free operating environment.

SUMMARY OF THE INVENTION

The purpose of the present invention is to solve the problems that traditional lithium ion batteries are toxic and flammable, and require anhydrous operating environment and lithium resource consumption, and provide a copper ion implanted zinc battery cathode material δ-manganese dioxide. Modification method.

A method for modifying δ-manganese dioxide, a positive electrode material of a zinc battery by implanting copper ions, is completed according to the following steps:

1. Preparation of δ-manganese dioxide powder:

①, first dissolve potassium permanganate in deionized water, then magnetically stir, then dropwise add hydrochloric acid, stir evenly, and obtain a mixed solution;

2. Transfer the mixed solution to the autoclave, then heat the autoclave to 130°C to 150°C, and then perform a hydrothermal reaction at 130°C to 150°C to obtain a precipitated substance;

3. First, use deionized water as the cleaning agent to centrifugally clean the precipitated material for 3 to 5 times, then use anhydrous ethanol as the cleaning agent to centrifugally clean the precipitated material for 3 to 5 times, and finally vacuum dry and cool to room temperature naturally. , to obtain δ-manganese dioxide powder;

2. ①. Add δ-manganese dioxide powder, conductive agent and binder to N-methylpyrrolidone, grind evenly, and obtain viscous electrode slurry;

②. Coat the viscous electrode slurry evenly on the current collector, and then vacuum dry to obtain the electrode sheet loaded with δ-manganese dioxide;

3. Copper ion implantation:

Using the mevva ion source, under the conditions of implantation energy of 50keV and dose of 5×10 ¹⁵ ions/cm ² , copper ions were implanted into the electrode sheet loaded with δ-manganese dioxide to obtain copper ion-implanted δ-manganese dioxide electrode sheet , that is, a method for modifying δ-manganese dioxide, which is a positive electrode material of a zinc battery by copper ion implantation, is completed.

Compared with the prior art, the present invention has the following beneficial technical effects:

1. The δ-manganese dioxide powder mainly prepared by the hydrothermal method in the present invention can be realized at a lower voltage because of its Mn ³⁺ /Mn ⁴⁺ redox pair, and it is easier to obtain Mn ⁴⁺ , so it can achieve a relatively low voltage. High specific capacity; and it is non-toxic, non-polluting, low cost, and wide source of raw materials, so the electrode sheet loaded with δ-manganese dioxide is used as a positive electrode material in an aqueous zinc-ion battery, not only a good capacity effect can be obtained. And the pollution to the environment has great advantages over traditional lithium-ion batteries;

2. The preparation process of δ-manganese dioxide is simple and the cost is low. Based on the doping technology of ion implantation, the interlayer spacing of δ-manganese dioxide is increased, the surface composition and properties of δ-manganese dioxide are optimized, and the δ-manganese dioxide is improved. The capacity of manganese can realize the storage of more zinc ions and improve the zinc storage performance of aqueous zinc ion batteries;

3. The performance of the aqueous zinc ion battery assembled with the copper ion-implanted δ-manganese dioxide electrode sheet prepared by the present invention is comparable to the performance of the aqueous zinc ion battery assembled with the copper ion-loaded δ-manganese dioxide electrode sheet without copper ion implantation. ratio, it has a high specific capacity of 519.4mAhg ^-1 at 0.1Ag ^-1 , while the aqueous zinc-ion battery assembled with the electrode sheet loaded with δ-manganese dioxide has a capacity of only 209.7mAhg ^-1 at the same current density, Meanwhile, at a current density of 1 A g ^-1 , the capacity remained at 119.2 mAhg ^-1 after 1000 cycles.

The δ-manganese dioxide electrode sheet implanted with copper ions of the present invention is used as a positive electrode material for a zinc battery.

Description of drawings

Fig. 1 is a XRD comparison diagram of the δ-manganese dioxide powder prepared in step 1 of Example 1 and the δ-manganese dioxide electrode sheet prepared by step 3 of Example 1 with copper ions implanted, and "■" in Fig. 1 is copper ion implantation The δ-manganese dioxide electrode sheet, "●" is δ-manganese dioxide;

Fig. 2 is a SEM image of the δ-manganese dioxide powder prepared in step 1 of Example 1. In Fig. 2 (a) is the morphology of manganese dioxide measured at a scale of 5 μm, and (b) is the morphology of manganese dioxide measured at a scale of 2 μm. The morphology of manganese oxide, (c) is the morphology of manganese dioxide measured at 1 μm scale, (d) is the morphology of manganese dioxide measured at 500 nm scale;

Fig. 3 is the Mapping diagram of the δ-manganese dioxide powder prepared in step 1 of Example 1, in Fig. 3 (a) is the corresponding scanning electron microscope image of the δ-manganese dioxide powder when Mapping is tested, and (b) is the distribution of manganese element Figure, (c) is the distribution diagram of oxygen element;

FIG. 4 is a mapping diagram of the copper ion-implanted δ-manganese dioxide electrode sheet prepared in step 3 of Example 1, and (a) in FIG. 4 is the corresponding scanning electron microscope when the copper ion-implanted δ-manganese dioxide electrode sheet is tested for Mapping Figure, (b) is the distribution diagram of manganese element, (c) is the distribution diagram of oxygen element, (d) is the distribution diagram of copper element;

Figure 5 is the first three CV curves of the aqueous zinc-ion battery assembled using the electrode sheet loaded with δ-manganese dioxide prepared in the second step of Example 1 in Comparative Example 2. In Figure 5, 1 ^st is the first circle, and 2 ^nd is the first circle. The second round, ^3rd is the third round;

Figure 6 is the first three ^CV curves of the aqueous zinc ion battery assembled using the copper ion-implanted δ-manganese dioxide electrode sheet prepared in the third step of the first embodiment in the second ^embodiment . is the second circle, ^3rd is the third circle;

Fig. 7 is a capacity comparison chart, "■" in Fig. 7 is the capacity of the aqueous zinc ion battery assembled with the electrode sheet loaded with δ-manganese dioxide prepared in the second step of Example 1 in Comparative Example 2, and "●" is the implementation In Example 2, the capacity of the aqueous zinc ion battery assembled with the copper ion-implanted δ-manganese dioxide electrode sheet prepared in step 3 of Example 1 is shown.

Detailed ways

The following examples further illustrate the content of the present invention, but should not be construed as limiting the present invention. Modifications and substitutions made to the methods, steps or conditions of the present invention without departing from the essence of the present invention all belong to the scope of the present invention.

Embodiment 1: In this embodiment, a method for modifying δ-manganese dioxide, which is a positive electrode material of a zinc battery by implanting copper ions, is completed according to the following steps:

1. Preparation of δ-manganese dioxide powder:

①, first dissolve potassium permanganate in deionized water, then magnetically stir, then dropwise add hydrochloric acid, stir evenly, and obtain a mixed solution;

2. Transfer the mixed solution to the autoclave, then heat the autoclave to 130°C to 150°C, and then perform a hydrothermal reaction at 130°C to 150°C to obtain a precipitated substance;

3. First, use deionized water as the cleaning agent to centrifugally clean the precipitated material for 3 to 5 times, then use anhydrous ethanol as the cleaning agent to centrifugally clean the precipitated material for 3 to 5 times, and finally vacuum dry and cool to room temperature naturally. , to obtain δ-manganese dioxide powder;

2. ①. Add δ-manganese dioxide powder, conductive agent and binder into N-methylpyrrolidone, grind evenly, and obtain a viscous electrode slurry;

②. Coat the viscous electrode slurry evenly on the current collector, and then vacuum dry to obtain the electrode sheet loaded with δ-manganese dioxide;

3. Copper ion implantation:

Using the mevva ion source, under the conditions of implantation energy of 50keV and dose of 5×10 ¹⁵ ions/cm ² , copper ions were implanted into the electrode sheet loaded with δ-manganese dioxide to obtain copper ion-implanted δ-manganese dioxide electrode sheet , that is, a method for modifying δ-manganese dioxide, which is a positive electrode material of a zinc battery by copper ion implantation, is completed.

The conductive agent described in step 2 ① of this embodiment is conductive graphite, and the binder is PVDF.

Embodiment 2: The difference between this embodiment and Embodiment 1 is: the amount of potassium permanganate described in step 1) and the volume ratio of deionized water are 1.25mmol: 34mL; step 1) The time of the magnetic stirring is 10min～20min. Other steps are the same as in the first embodiment.

Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is: the concentration of hydrochloric acid described in step 1 1 is 5mmol/L; the volume ratio of hydrochloric acid and deionized water described in step 1 1 0.416mL:34mL. Other steps are the same as in the first or second embodiment.

Embodiment 4: This embodiment differs from Embodiments 1 to 3 in that the time of the hydrothermal reaction at 130°C to 150°C in step 1 (2) is 0.5h to 1h. The other steps are the same as those in the first to third embodiments.

Embodiment 5: The difference between this embodiment and Embodiments 1 to 4 is that the temperature of vacuum drying in step 1 (3) is 60°C, and the time of vacuum drying is 10h-12h. The other steps are the same as those in the first to fourth embodiments.

Embodiment 6: The difference between this embodiment and Embodiments 1 to 5 is that the mass ratio of the δ-manganese dioxide powder, conductive agent and binder described in step 2 ① is 14:4:2. Other steps are the same as those of the specific embodiments 1 to 5.

Embodiment 7: The difference between this embodiment and Embodiments 1 to 6 is that the mass ratio of the δ-manganese dioxide powder described in step 2 ① to the volume of N-methylpyrrolidone is 7 mg:0.2 mL. Other steps are the same as those of the specific embodiments 1 to 6.

Embodiment 8: This embodiment differs from Embodiments 1 to 7 in that: the temperature of vacuum drying described in step 2 ② is 60°C to 80°C; the current collector described in step 2 2 has a diameter of 12-14mm stainless steel mesh. Other steps are the same as those in the specific embodiments 1 to 7.

Embodiment 9: The difference between this embodiment and Embodiments 1 to 8 is that the assembly of an aqueous zinc ion battery using a delta-manganese dioxide electrode sheet implanted with copper ions is completed according to the following steps:

The battery can be assembled directly in the air, with zinc sheet as the negative electrode and manganese sulfate/zinc sulfate aqueous solution as the electrolyte, according to: positive electrode shell - gasket - δ-manganese dioxide electrode sheet injected with copper ions - diaphragm - zinc sheet - The order of the negative electrode shell, assemble the 2025 button battery from top to bottom, drip the electrolyte to completely wet the positive electrode sheet and the diaphragm, then use a battery sealing machine to seal, and stand to activate to obtain a water-based zinc ion battery. Other steps are the same as those of the specific embodiments 1 to 8.

Embodiment 10: The difference between this embodiment and Embodiments 1 to 9 is: the manganese sulfate/zinc sulfate aqueous solution is the manganese sulfate aqueous solution of 0.1 mol/L and the zinc sulfate aqueous solution of 2 mol/L according to the volume ratio of 1 : 20 mixed; the activation time is 8h～10h. Other steps are the same as those of the specific embodiments 1 to 9.

Adopt the following examples to verify the beneficial effects of the present invention:

Embodiment 1: A method for modifying δ-manganese dioxide, a positive electrode material of a zinc battery by implanting copper ions, is completed according to the following steps:

1. Preparation of δ-manganese dioxide powder:

1. First, dissolve 1.25 mmol potassium permanganate in 34 mL of deionized water, then magnetically stir for 15 min, and then dropwise add 0.416 mL of hydrochloric acid with a concentration of 12 mol/L, and stir evenly to obtain a mixed solution;

2. Transfer the mixed solution to the autoclave, then heat the autoclave to 140°C, and then perform a hydrothermal reaction at 140°C to obtain a precipitated substance;

The time of hydrothermal reaction at 140°C in step 1 and 2 is 0.5h;

3. First, use deionized water as the cleaning agent to centrifugally clean the precipitated material for 3 times, then use absolute ethanol as the cleaning agent to centrifugally clean the precipitated material for 3 times, and finally vacuum dry it at 60 °C for 10 hours, and naturally cool it to room temperature , to obtain δ-manganese dioxide powder;

2. ①. Add δ-manganese dioxide powder, conductive agent and binder to N-methylpyrrolidone, grind evenly, and obtain viscous electrode slurry;

The mass ratio of the δ-manganese dioxide powder, conductive agent and binder described in step 2 ① is 14:4:2;

The volume ratio of the mass of δ-manganese dioxide powder described in step 2 1. to N-methylpyrrolidone is 7mg:0.2mL;

The conductive agent described in step 2 1 is conductive graphite, and the binder is PVDF;

②. Coat the viscous electrode slurry evenly on the current collector, and then vacuum dry to obtain the electrode sheet loaded with δ-manganese dioxide;

The temperature of vacuum drying described in step 2 2 is 70°C; the current collector described in step 2 2 is a stainless steel mesh with a diameter of 13 mm;

3. Copper ion implantation:

Using the mevva ion source, under the conditions of implantation energy of 50keV and dose of 5×10 ¹⁵ ions/cm ² , copper ions were implanted into the electrode sheet loaded with δ-manganese dioxide to obtain copper ion-implanted δ-manganese dioxide electrode sheet , that is, a method for modifying δ-manganese dioxide, which is a positive electrode material of a zinc battery by copper ion implantation, is completed.

The experiment of implanting copper ions in step 3 of Example 1 was done in the Key Laboratory of Ray Beam Technology, Ministry of Education, Beijing Normal University.

Example 2: Using the copper ion-implanted δ-manganese dioxide electrode sheet prepared in step 3 of Example 1 to assemble an aqueous zinc ion battery is completed according to the following steps:

The battery can be assembled directly in the air, with zinc sheet as the negative electrode, with manganese sulfate/zinc sulfate aqueous solution as the electrolyte, according to: positive electrode shell-gasket-the delta-manganese dioxide injected with copper ions prepared in step 3 of Example 1 The order of electrode sheet-diaphragm-zinc sheet-negative electrode shell is assembled from top to bottom into a 2025 button battery, dripping electrolyte, so that the positive electrode sheet and the diaphragm are completely wetted, and then sealed with a battery sealing machine, and left to activate to obtain Aqueous zinc-ion battery.

The manganese sulfate/zinc sulfate aqueous solution is formed by mixing 3 mol/L manganese sulfate aqueous solution and 1 mol/L zinc sulfate aqueous solution according to a volume ratio of 1:3; the activation time is 8h.

Comparative Example 2: Using the electrode sheet loaded with δ-manganese dioxide prepared in Step 2 of Example 1 to assemble an aqueous zinc-ion battery is completed according to the following steps:

The battery can be assembled directly in the air, with zinc sheet as the negative electrode, with manganese sulfate/zinc sulfate aqueous solution as the electrolyte, according to: positive electrode shell-gasket-loaded δ-manganese dioxide-loaded electrode sheet prepared in step 2 of Example 1 - The order of diaphragm - zinc sheet - negative electrode shell, assemble a 2025 button battery from top to bottom, add electrolyte dropwise to completely wet the positive electrode sheet and the diaphragm, then use a battery sealing machine to seal, stand for activation, and obtain water-based zinc ion battery.

The manganese sulfate/zinc sulfate aqueous solution is formed by mixing 0.1 mol/L manganese sulfate aqueous solution and 2 mol/L zinc sulfate aqueous solution according to a volume ratio of 1:20; the activation time is 8h.

Fig. 1 is a XRD comparison diagram of the δ-manganese dioxide powder prepared in step 1 of Example 1 and the δ-manganese dioxide electrode sheet prepared by step 3 of Example 1 with copper ions implanted, and "■" in Fig. 1 is copper ion implantation The δ-manganese dioxide electrode sheet, "●" is δ-manganese dioxide;

It can be seen from Fig. 1 that the powder prepared by the present invention is δ-manganese dioxide powder.

Fig. 2 is a SEM image of the δ-manganese dioxide powder prepared in step 1 of Example 1. In Fig. 2 (a) is the morphology of manganese dioxide measured at a scale of 5 μm, and (b) is the morphology of manganese dioxide measured at a scale of 2 μm. The morphology of manganese oxide, (c) is the morphology of manganese dioxide measured at 1 μm scale, (d) is the morphology of manganese dioxide measured at 500 nm scale;

It can be seen from FIG. 2 that the δ-manganese dioxide powder prepared by the present invention has a known sea urchin-like layered structure.

Fig. 3 is the Mapping diagram of the δ-manganese dioxide powder prepared in step 1 of Example 1, in Fig. 3 (a) is the corresponding scanning electron microscope image of the δ-manganese dioxide powder when Mapping is tested, and (b) is the distribution of manganese element Figure, (c) is the distribution diagram of oxygen element;

It can be seen from FIG. 3 that the δ-manganese dioxide powder prepared by the present invention is composed of two elements, manganese and oxygen, respectively.

Figure 4 shows the mapping diagram of the pole piece carrying δ-manganese dioxide powder prepared in step 3 of Example 1 after implanting copper ions;

FIG. 4 is a mapping diagram of the copper ion-implanted δ-manganese dioxide electrode sheet prepared in step 3 of Example 1, and (a) in FIG. 4 is the corresponding scanning electron microscope when the copper ion-implanted δ-manganese dioxide electrode sheet is tested for Mapping Figure, (b) is the distribution diagram of manganese element, (c) is the distribution diagram of oxygen element, (d) is the distribution diagram of copper element;

It can be seen from FIG. 4 that the pole piece bearing δ-manganese dioxide powder prepared by the present invention is mainly composed of three elements, manganese, oxygen and copper, after the copper ions are implanted.

Figure 5 is the first three CV curves of the aqueous zinc-ion battery assembled using the electrode sheet loaded with δ-manganese dioxide prepared in the second step of Example 1 in Comparative Example 2. In Figure 5, 1 ^st is the first circle, and 2 ^nd is the first circle. The second round, ^3rd is the third round;

It can be seen from FIG. 5 that the water-based zinc ion battery assembled with the δ-manganese dioxide powder prepared by the present invention undergoes a redox reaction during the charging and discharging process, and the potential of the reaction is consistent with the known literature.

Figure 6 is the first three ^CV curves of the aqueous zinc ion battery assembled using the copper ion-implanted δ-manganese dioxide electrode sheet prepared in the third step of the first embodiment in the second ^embodiment . is the second circle, ^3rd is the third circle;

It can be seen from FIG. 6 that the water-based zinc ion battery assembled with the copper ion-implanted δ-manganese dioxide prepared by the present invention undergoes a redox reaction during the charge and discharge process, and the potential of the reaction is consistent with the known literature.

Fig. 7 is a capacity comparison chart, "■" in Fig. 7 is the capacity of the aqueous zinc ion battery assembled with the electrode sheet loaded with δ-manganese dioxide prepared in the second step of Example 1 in Comparative Example 2, and "●" is the implementation In Example 2, the capacity of the aqueous zinc ion battery assembled with the copper ion-implanted δ-manganese dioxide electrode sheet prepared in Step 3 of Example 1;

As can be seen from FIG. 7 , the performance of the aqueous zinc ion battery assembled with the copper ion-implanted δ-manganese dioxide electrode sheet prepared in step 3 of embodiment 1 in Example 2 is the same as that of Comparative Example 2 prepared by using Step 2 of Example 1 It has a high specific capacity of 519.4mAh g ^-1 at 0.1A g ^-1 compared to the aqueous zinc-ion battery assembled with δ-manganese dioxide-loaded electrode sheets, while the δ-manganese dioxide-loaded electrode sheets assembled with At the same current density, the aqueous zinc-ion battery has a capacity of only 209.7mAh g ^-1 . It can be seen that the capacity of the aqueous zinc ion battery assembled by the copper ion implanted δ-manganese dioxide electrode sheet prepared by the present invention is significantly improved after the copper ion implantation.

Claims (10)

1. a method for modifying copper ions into zinc battery positive material δ-manganese dioxide, it is characterized in that a copper ion implants into zinc battery positive material δ-manganese dioxide for the modification method is completed according to the following steps: 1. Preparation of δ-manganese dioxide powder: ①, first dissolve potassium permanganate in deionized water, then magnetically stir, then dropwise add hydrochloric acid, stir evenly, and obtain a mixed solution; 2. Transfer the mixed solution to the autoclave, then heat the autoclave to 130°C to 150°C, and then perform a hydrothermal reaction at 130°C to 150°C to obtain a precipitated substance; 3. First, use deionized water as the cleaning agent to centrifugally clean the precipitated material for 3 to 5 times, then use anhydrous ethanol as the cleaning agent to centrifugally clean the precipitated material for 3 to 5 times, and finally vacuum dry and cool to room temperature naturally. , to obtain δ-manganese dioxide powder; 2. ①. Add δ-manganese dioxide powder, conductive agent and binder to N-methylpyrrolidone, grind evenly, and obtain viscous electrode slurry; ②. Coat the viscous electrode slurry evenly on the current collector, and then vacuum dry to obtain the electrode sheet loaded with δ-manganese dioxide; 3. Copper ion implantation: Using the mevva ion source, under the conditions of implantation energy of 50keV and dose of 5×10 ¹⁵ ions/cm ² , copper ions were implanted into the electrode sheet loaded with δ-manganese dioxide to obtain copper ion-implanted δ-manganese dioxide electrode sheet , that is, a method for modifying δ-manganese dioxide, which is a positive electrode material of a zinc battery by copper ion implantation, is completed. 2. the modification method of a kind of copper ion implantation zinc battery positive electrode material δ-manganese dioxide according to claim 1, is characterized in that the amount of substance of potassium permanganate described in step 1 1. and deionized water The volume ratio is 1.25 mmol: 34 mL; the time of magnetic stirring described in step 1 ① is 10 min to 20 min. 3. the modification method of a kind of copper ion implantation zinc battery positive electrode material δ-manganese dioxide according to claim 1, it is characterized in that the concentration of the hydrochloric acid described in step 1 1. is 5mmol/L; step 1 1. in The volume ratio of the hydrochloric acid and deionized water is 0.416mL:34mL. 4. The method for modifying δ-manganese dioxide, which is a positive electrode material of a zinc battery by implanting copper ions into a zinc battery according to claim 1, characterized in that in step 1 (2), the hydrothermal reaction time at 130°C to 150°C is 0.5h to 0.5h. 1h. 5. the modification method of a kind of copper ion implantation zinc battery positive electrode material δ-manganese dioxide according to claim 1, it is characterized in that the temperature of vacuum drying described in step 1 ③ is 60 ℃, the time of vacuum drying For 10h ~ 12h. 6. The method for modifying the δ-manganese dioxide of a copper ion-implanted zinc battery positive electrode material according to claim 1, characterized in that the δ-manganese dioxide powder, conductive agent and bonding described in step 2 1. The mass ratio of the agent is 14:4:2. 7. A method for modifying the δ-manganese dioxide of a copper ion implanted positive electrode material of a zinc battery according to claim 1, wherein the mass of the δ-manganese dioxide powder and the volume of N-methylpyrrolidone described in step 2 1. The ratio was 7 mg:0.2 mL. 8. The method for modifying δ-manganese dioxide, which is a positive electrode material of a zinc battery by implanting copper ions into a zinc battery according to claim 1, wherein the temperature of the vacuum drying described in step 2 ② is 60°C to 80°C; step The current collector described in 2 ② is a stainless steel mesh with a diameter of 12 to 14 mm. 9. the modification method of a kind of copper ion implantation zinc battery positive electrode material δ-manganese dioxide according to claim 1, it is characterized in that using the δ-manganese dioxide electrode sheet of copper ion implantation to assemble the aqueous zinc ion battery is to press The following steps are done: The battery can be assembled directly in the air, with zinc sheet as the negative electrode and manganese sulfate/zinc sulfate aqueous solution as the electrolyte, according to: positive electrode shell - gasket - δ-manganese dioxide electrode sheet injected with copper ions - diaphragm - zinc sheet - The order of the negative electrode shell, assemble the 2025 button battery from top to bottom, drip the electrolyte to completely wet the positive electrode sheet and the diaphragm, then use a battery sealer to seal, and stand to activate to obtain a water-based zinc ion battery. 10. The modification method of a kind of copper ion implantation zinc battery positive electrode material δ-manganese dioxide according to claim 9, it is characterized in that described manganese sulfate/zinc sulfate aqueous solution is the manganese sulfate aqueous solution of 0.1mol/L and The 2mol/L zinc sulfate aqueous solution is mixed according to the volume ratio of 1:20; the activation time is 8h to 10h.

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