CN114314670A - Modification method of copper ion implanted zinc battery anode material delta-manganese dioxide - Google Patents
Modification method of copper ion implanted zinc battery anode material delta-manganese dioxide Download PDFInfo
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Abstract
A modification method of copper ion implantation zinc battery anode material delta-manganese dioxide relates to a preparation method of battery anode material. The invention aims to solve the problems that the traditional lithium ion battery is toxic and inflammable, needs a waterless operation environment and consumes more lithium resources. The method comprises the following steps: firstly, preparing delta-manganese dioxide powder; secondly, preparing viscous electrode slurry; and thirdly, copper ion implantation. Compared with the performance of the water-based zinc ion battery assembled by the delta-manganese dioxide electrode plate without copper ion injection, the performance of the water-based zinc ion battery assembled by the copper ion injection delta-manganese dioxide electrode plate prepared by the invention is 0.1Ag‑1It has 519.4mAhg‑1The capacity of the water-based zinc ion battery assembled by electrode plates loaded with delta-manganese dioxide is only 209.7mAhg under the same current density‑1。
Description
Technical Field
The invention relates to a preparation method of a battery positive electrode material.
Background
Energy and environment are two major problems which need to be dealt with in the current human survival and social development, along with the rapid development of science and technology, the rapid consumption of energy is provided, but fossil energy such as coal, petroleum and the like is inexhaustible, meanwhile, the climate and environment are increasingly worsened, which is contrary to the green and healthy life pursued by human, so the development of renewable energy such as solar energy, wind energy and the like has become a global trend. However, these renewable natural energy sources are affected by uncontrollable factors such as weather and geography, and thus cannot be widely used in daily life. Therefore, the application of energy storage devices is critical to overcome these challenges, and currently widely used lithium ion batteries, while having many advantages, are not only toxic, flammable, but also require a non-aqueous operating environment
Disclosure of Invention
The invention aims to solve the problems that the traditional lithium ion battery is toxic and flammable, needs a waterless operation environment and consumes a large amount of lithium resources, and provides a method for modifying a positive electrode material delta-manganese dioxide of a zinc battery by injecting copper ions.
A modification method of copper ion injection zinc battery anode material delta-manganese dioxide is completed according to the following steps:
firstly, preparing delta-manganese dioxide powder:
firstly, dissolving potassium permanganate in deionized water, then stirring by magnetic force, then dripping hydrochloric acid, and stirring uniformly to obtain a mixed solution;
secondly, transferring the mixed solution into a high-pressure reaction kettle, heating the high-pressure reaction kettle to 130-150 ℃, and carrying out hydrothermal reaction at 130-150 ℃ to obtain a precipitate;
centrifugally cleaning the sediment for 3-5 times by using deionized water as a cleaning agent, centrifugally cleaning the sediment for 3-5 times by using absolute ethyl alcohol as a cleaning agent, and finally drying in vacuum and naturally cooling to room temperature to obtain delta-manganese dioxide powder;
adding delta-manganese dioxide powder, a conductive agent and a binder into N-methyl pyrrolidone, and uniformly grinding to obtain viscous electrode slurry;
uniformly coating the viscous electrode slurry on a current collector, and then drying in vacuum to obtain an electrode slice loaded with delta-manganese dioxide;
thirdly, copper ion implantation:
using a mevva ion source at an implant energy of 50keV and a dose of 5X 1015ions/cm2Under the condition of (1), injecting copper ions into the delta-manganese dioxide loaded electrode slice to obtain the delta-manganese dioxide electrode slice with copper ions injected, namely completing the method for modifying the delta-manganese dioxide anode material of the copper ion injection zinc battery.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention mainly uses delta-manganese dioxide powder prepared by a hydrothermal method, because of Mn thereof3+/Mn4+The redox couple can be realized at lower voltage and Mn is obtained4+Is easier, thus realizing higher specific capacity; the electrode plate loaded with delta-manganese dioxide is used as a positive electrode material to be applied to a water-system zinc ion battery, so that a good capacity effect can be obtained, and the pollution to the environment is greatly superior to that of a traditional lithium ion battery;
secondly, the preparation process flow of the delta-manganese dioxide is simple, the cost is low, the interlayer spacing of the delta-manganese dioxide is increased, the surface component and the performance of the delta-manganese dioxide are optimized, the capacity of the delta-manganese dioxide is improved, the storage of more zinc ions is realized, and the zinc storage performance of the water system zinc ion battery is improved based on the ion implantation doping technology;
thirdly, compared with the performance of the water-based zinc ion battery assembled by the delta-manganese dioxide electrode plate without copper ion injection, the performance of the water-based zinc ion battery assembled by the copper ion injection delta-manganese dioxide electrode plate prepared by the invention is 0.1Ag-1It has 519.4mAhg-1The capacity of the water-based zinc ion battery assembled by electrode plates loaded with delta-manganese dioxide is only 209.7mAhg under the same current density-1At the same time, at 1A g-1After 1000 cycles, the capacity remains atBut maintained at 119.2mAhg-1。
The delta-manganese dioxide electrode plate injected with copper ions is used as a positive electrode material of a zinc battery.
Drawings
Fig. 1 is an XRD comparison graph of the delta-manganese dioxide powder prepared in one step one of the examples and the copper ion implanted delta-manganese dioxide electrode sheet prepared in one step three of the examples, where "■" in fig. 1 is the copper ion implanted delta-manganese dioxide electrode sheet and "●" is delta-manganese dioxide;
fig. 2 is an SEM image of the delta-manganese dioxide powder prepared at one step one of the examples, wherein in fig. 2, (a) is the morphology of manganese dioxide measured at the 5 μm scale, (b) is the morphology of manganese dioxide measured at the 2 μm scale, (c) is the morphology of manganese dioxide measured at the 1 μm scale, and (d) is the morphology of manganese dioxide measured at the 500nm scale;
FIG. 3 is a Mapping diagram of delta-manganese dioxide powder prepared in one step one of the examples, wherein (a) is a scanning electron microscope diagram corresponding to the delta-manganese dioxide powder testing Mapping, (b) is a distribution diagram of manganese element, and (c) is a distribution diagram of oxygen element in FIG. 3;
fig. 4 is a Mapping diagram of a copper ion implanted delta-manganese dioxide electrode plate prepared in the third step of the example, wherein (a) in fig. 4 is a scanning electron microscope diagram corresponding to the copper ion implanted delta-manganese dioxide electrode plate when testing Mapping, (b) is a distribution diagram of manganese element, (c) is a distribution diagram of oxygen element, and (d) is a distribution diagram of copper element;
FIG. 5 is the front three-turn CV curve of an aqueous zinc-ion battery assembled using delta-manganese dioxide-loaded electrode sheets prepared in one step two of example in a comparative example two, 1 in FIG. 5stIs the first turn, 2ndIs the second turn, 3rdIs the third circle;
FIG. 6 is the front three-turn CV curve of an aqueous zinc ion battery assembled using copper ion-implanted delta-manganese dioxide electrode tabs prepared in step three of example two, FIG. 6, item 1stIs the first turn, 2ndIs the second turn, 3rdIs the third circle;
fig. 7 is a graph showing capacity comparison, where "■" in fig. 7 shows the capacity of the aqueous zinc-ion battery assembled using the δ -manganese dioxide-loaded electrode tab prepared in one step two of the example in the second comparative example, and "●" shows the capacity of the aqueous zinc-ion battery assembled using the δ -manganese dioxide electrode tab prepared in one step three of the example in the second example, in which copper ions are injected.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the modification method of copper ion implanted zinc battery anode material delta-manganese dioxide in the embodiment is completed according to the following steps:
firstly, preparing delta-manganese dioxide powder:
firstly, dissolving potassium permanganate in deionized water, then stirring by magnetic force, then dripping hydrochloric acid, and stirring uniformly to obtain a mixed solution;
secondly, transferring the mixed solution into a high-pressure reaction kettle, heating the high-pressure reaction kettle to 130-150 ℃, and carrying out hydrothermal reaction at 130-150 ℃ to obtain a precipitate;
centrifugally cleaning the sediment for 3-5 times by using deionized water as a cleaning agent, centrifugally cleaning the sediment for 3-5 times by using absolute ethyl alcohol as a cleaning agent, and finally drying in vacuum and naturally cooling to room temperature to obtain delta-manganese dioxide powder;
adding delta-manganese dioxide powder, a conductive agent and a binder into N-methyl pyrrolidone, and uniformly grinding to obtain viscous electrode slurry;
uniformly coating the viscous electrode slurry on a current collector, and then drying in vacuum to obtain an electrode slice loaded with delta-manganese dioxide;
thirdly, copper ion implantation:
using a mevva ion source at an implant energy of 50keV and a dose of 5X 1015ions/cm2Under the condition of (1), injecting copper ions into the electrode plate loaded with delta-manganese dioxide to obtain copper ion injected delta-dioxideThe manganese electrode slice is used for finishing a method for modifying the positive electrode material delta-manganese dioxide of the zinc battery by injecting copper ions.
In the second step of the present embodiment, the conductive agent is conductive graphite, and the binder is PVDF.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the volume ratio of the potassium permanganate substance in the first step to the deionized water is 1.25mmol:34 mL; the magnetic stirring time in the first step is 10-20 min. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the concentration of the hydrochloric acid in the first step is 5 mmol/L; the volume ratio of the hydrochloric acid to the deionized water in the first step is 0.416mL to 34 mL. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: in the first step, the hydrothermal reaction time is 0.5-1 h at 130-150 ℃. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the temperature of the vacuum drying in the step one is 60 ℃, and the time of the vacuum drying is 10-12 h. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: and the mass ratio of the delta-manganese dioxide powder, the conductive agent and the binder in the second step is 14:4: 2. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and the volume ratio of the mass of the delta-manganese dioxide powder to the volume of the N-methyl pyrrolidone in the second step is 7mg to 0.2 mL. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the temperature of the vacuum drying in the second step is 60-80 ℃; and in the second step, the current collector is a stainless steel net with the diameter of 12-14 mm. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the assembly of the water-based zinc ion battery by using the delta-manganese dioxide electrode plate injected with copper ions is completed according to the following steps:
the battery can be directly assembled in the air, a zinc sheet is taken as a negative electrode, a manganese sulfate/zinc sulfate aqueous solution is taken as electrolyte, and the method comprises the following steps: assembling a 2025 button cell from top to bottom by the sequence of a positive electrode shell, a gasket, a delta-manganese dioxide electrode plate injected with copper ions, a diaphragm, a zinc plate and a negative electrode shell, dripping electrolyte to completely wet the positive electrode plate and the diaphragm, sealing by using a cell sealing machine, standing and activating to obtain the water-based zinc ion cell. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: the manganese sulfate/zinc sulfate aqueous solution is formed by mixing 0.1mol/L manganese sulfate aqueous solution and 2mol/L zinc sulfate aqueous solution according to the volume ratio of 1: 20; the activation time is 8-10 h. The other steps are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: a modification method of copper ion injection zinc battery anode material delta-manganese dioxide is completed according to the following steps:
firstly, preparing delta-manganese dioxide powder:
firstly, dissolving 1.25mmol of potassium permanganate in 34mL of deionized water, then magnetically stirring for 15min, then dripping 0.416mL of hydrochloric acid with the concentration of 12mol/L, and uniformly stirring to obtain a mixed solution;
transferring the mixed solution into a high-pressure reaction kettle, heating the high-pressure reaction kettle to 140 ℃, and carrying out hydrothermal reaction at 140 ℃ to obtain a precipitate;
in the first step, the hydrothermal reaction time is 0.5h at 140 ℃;
centrifugally cleaning the sediment for 3 times by using deionized water as a cleaning agent, centrifugally cleaning the sediment for 3 times by using absolute ethyl alcohol as a cleaning agent, finally drying the sediment for 10 hours in vacuum at the temperature of 60 ℃, and naturally cooling the sediment to room temperature to obtain delta-manganese dioxide powder;
adding delta-manganese dioxide powder, a conductive agent and a binder into N-methyl pyrrolidone, and uniformly grinding to obtain viscous electrode slurry;
the mass ratio of the delta-manganese dioxide powder, the conductive agent and the binder in the second step is 14:4: 2;
the volume ratio of the mass of the delta-manganese dioxide powder to the volume of the N-methyl pyrrolidone in the second step is 7mg to 0.2 mL;
the conductive agent in the second step is conductive graphite, and the binder is PVDF;
uniformly coating the viscous electrode slurry on a current collector, and then drying in vacuum to obtain an electrode slice loaded with delta-manganese dioxide;
the temperature of the vacuum drying in the second step is 70 ℃; the current collector in the second step is a stainless steel net with the diameter of 13 mm;
thirdly, copper ion implantation:
using a mevva ion source at an implant energy of 50keV and a dose of 5X 1015ions/cm2Under the condition of (1), injecting copper ions into the delta-manganese dioxide loaded electrode slice to obtain the delta-manganese dioxide electrode slice with copper ions injected, namely completing the method for modifying the delta-manganese dioxide anode material of the copper ion injection zinc battery.
Example a test for copper ion implantation in step three was conducted in the key laboratory of the department of beam technology education at university of beijing teachers.
Example two: the assembly of an aqueous zinc ion battery using the copper ion-implanted delta-manganese dioxide electrode sheet prepared in step three of the example was carried out as follows:
the battery can be directly assembled in the air, a zinc sheet is taken as a negative electrode, a manganese sulfate/zinc sulfate aqueous solution is taken as electrolyte, and the method comprises the following steps: the sequence of the positive electrode shell, the gasket, the delta-manganese dioxide electrode plate with copper ions injected, the diaphragm, the zinc plate and the negative electrode shell prepared in the third step of the example is assembled into a 2025 button cell from top to bottom, the electrolyte is dripped to completely wet the positive electrode plate and the diaphragm, then a cell sealing machine is used for sealing, and standing and activation are carried out to obtain the water-based zinc ion cell.
The manganese sulfate/zinc sulfate aqueous solution is formed by mixing 3mol/L of manganese sulfate aqueous solution and 1mol/L of zinc sulfate aqueous solution according to the volume ratio of 1: 3; the activation time is 8 h.
Comparative example two: the assembly of the aqueous zinc-ion battery using the delta-manganese dioxide-loaded electrode sheet prepared in the second step of the example was carried out as follows:
the battery can be directly assembled in the air, a zinc sheet is taken as a negative electrode, a manganese sulfate/zinc sulfate aqueous solution is taken as electrolyte, and the method comprises the following steps: the sequence of the positive electrode shell, the gasket, the electrode plate loaded with delta-manganese dioxide prepared in the second step of the example, the diaphragm, the zinc plate and the negative electrode shell is assembled into a 2025 button cell from top to bottom, the electrolyte is dripped to completely wet the positive electrode plate and the diaphragm, then a cell sealing machine is used for sealing, and standing and activation are carried out to obtain the water-based zinc ion cell.
The manganese sulfate/zinc sulfate aqueous solution is formed by mixing 0.1mol/L manganese sulfate aqueous solution and 2mol/L zinc sulfate aqueous solution according to the volume ratio of 1: 20; the activation time is 8 h.
Fig. 1 is an XRD comparison graph of the delta-manganese dioxide powder prepared in one step one of the examples and the copper ion implanted delta-manganese dioxide electrode sheet prepared in one step three of the examples, where "■" in fig. 1 is the copper ion implanted delta-manganese dioxide electrode sheet and "●" is delta-manganese dioxide;
as can be seen from fig. 1; the powder produced by the present invention is delta-manganese dioxide powder.
Fig. 2 is an SEM image of the delta-manganese dioxide powder prepared at one step one of the examples, wherein in fig. 2, (a) is the morphology of manganese dioxide measured at the 5 μm scale, (b) is the morphology of manganese dioxide measured at the 2 μm scale, (c) is the morphology of manganese dioxide measured at the 1 μm scale, and (d) is the morphology of manganese dioxide measured at the 500nm scale;
as can be seen from fig. 2, the delta-manganese dioxide powder produced by the present invention is a known sea urchin-like layered structure.
FIG. 3 is a Mapping diagram of delta-manganese dioxide powder prepared in one step one of the examples, wherein (a) is a scanning electron microscope diagram corresponding to the delta-manganese dioxide powder testing Mapping, (b) is a distribution diagram of manganese element, and (c) is a distribution diagram of oxygen element in FIG. 3;
as can be seen from fig. 3, the delta-manganese dioxide powder prepared by the present invention is composed of two elements, manganese and oxygen, respectively.
The Mapping graph of the delta-manganese dioxide powder loaded electrode sheet prepared in step three of the example after copper ion implantation is shown in fig. 4;
fig. 4 is a Mapping diagram of a copper ion implanted delta-manganese dioxide electrode plate prepared in the third step of the example, wherein (a) in fig. 4 is a scanning electron microscope diagram corresponding to the copper ion implanted delta-manganese dioxide electrode plate when testing Mapping, (b) is a distribution diagram of manganese element, (c) is a distribution diagram of oxygen element, and (d) is a distribution diagram of copper element;
as can be seen from fig. 4, the delta-manganese dioxide powder loaded pole pieces made by the present invention were comprised primarily of manganese, oxygen, and copper after copper ion implantation.
FIG. 5 is the front three-turn CV curve of an aqueous zinc-ion battery assembled using delta-manganese dioxide-loaded electrode sheets prepared in one step two of example in a comparative example two, 1 in FIG. 5stIs the first turn, 2ndIs the second turn, 3rdIs the third circle;
as is clear from fig. 5, the aqueous zinc ion battery assembled with the δ -manganese dioxide powder produced by the present invention undergoes an oxidation-reduction reaction during charge and discharge, and the potential at which the reaction occurs is consistent with that of the known literature.
FIG. 6 is the front three-turn CV curve of an aqueous zinc ion battery assembled using copper ion-implanted delta-manganese dioxide electrode tabs prepared in step three of example two, FIG. 6, item 1stIs the first turn, 2ndIs the second turn, 3rdIs the third circle;
as is clear from fig. 6, the aqueous zinc ion battery assembled with δ -manganese dioxide impregnated with copper ions produced by the present invention undergoes redox reaction during charge and discharge, and the potential at which the reaction occurs is consistent with that of the known literature.
Fig. 7 is a graph comparing capacities, where "■" in fig. 7 is the capacity of the aqueous zinc-ion battery assembled using the delta-manganese dioxide-loaded electrode tab prepared in one step two of example in comparative example two, and "●" is the capacity of the aqueous zinc-ion battery assembled using the copper ion-implanted delta-manganese dioxide electrode tab prepared in one step three of example in example two;
as can be seen from fig. 7, the performance of the aqueous zinc ion battery assembled using the copper ion-implanted δ -manganese dioxide electrode sheet prepared in example two by the third step of example was 0.1A g, compared to the aqueous zinc ion battery assembled using the δ -manganese dioxide-loaded electrode sheet prepared in comparative example two by the second step of example-1It has 519.4mAh g-1The capacity of the water system zinc ion battery assembled by electrode plates loaded with delta-manganese dioxide is only 209.7mAh g under the same current density-1. From this, it is understood that the capacity of the aqueous zinc ion battery assembled with the copper ion-implanted δ -manganese dioxide electrode sheet obtained in the present invention is significantly improved after the copper ion implantation.
Claims (10)
1. A modification method of copper ion implantation zinc battery anode material delta-manganese dioxide is characterized in that the modification method of copper ion implantation zinc battery anode material delta-manganese dioxide is completed according to the following steps:
firstly, preparing delta-manganese dioxide powder:
firstly, dissolving potassium permanganate in deionized water, then stirring by magnetic force, then dripping hydrochloric acid, and stirring uniformly to obtain a mixed solution;
secondly, transferring the mixed solution into a high-pressure reaction kettle, heating the high-pressure reaction kettle to 130-150 ℃, and carrying out hydrothermal reaction at 130-150 ℃ to obtain a precipitate;
centrifugally cleaning the sediment for 3-5 times by using deionized water as a cleaning agent, centrifugally cleaning the sediment for 3-5 times by using absolute ethyl alcohol as a cleaning agent, and finally drying in vacuum and naturally cooling to room temperature to obtain delta-manganese dioxide powder;
adding delta-manganese dioxide powder, a conductive agent and a binder into N-methyl pyrrolidone, and uniformly grinding to obtain viscous electrode slurry;
uniformly coating the viscous electrode slurry on a current collector, and then drying in vacuum to obtain an electrode slice loaded with delta-manganese dioxide;
thirdly, copper ion implantation:
using a mevva ion source at an implant energy of 50keV and a dose of 5X 1015ions/cm2Under the condition of (1), injecting copper ions into the delta-manganese dioxide loaded electrode slice to obtain the delta-manganese dioxide electrode slice with copper ions injected, namely completing the method for modifying the delta-manganese dioxide anode material of the copper ion injection zinc battery.
2. The method for modifying the copper ion-implanted zinc battery positive electrode material delta-manganese dioxide according to claim 1, wherein the volume ratio of the amount of potassium permanganate to deionized water in the first step is 1.25mmol:34 mL; the magnetic stirring time in the first step is 10-20 min.
3. The method for modifying delta-manganese dioxide used as the positive electrode material of the copper ion injection zinc battery according to claim 1, wherein the concentration of hydrochloric acid in the first step is 5 mmol/L; the volume ratio of the hydrochloric acid to the deionized water in the first step is 0.416mL to 34 mL.
4. The method for modifying delta-manganese dioxide as the positive electrode material of the copper ion-implanted zinc battery according to claim 1, wherein the hydrothermal reaction time in the first step is 0.5 to 1 hour at 130 to 150 ℃.
5. The method for modifying the positive electrode material delta-manganese dioxide of the copper ion implanted zinc battery according to claim 1, wherein the temperature of the vacuum drying in the step one is 60 ℃, and the time of the vacuum drying is 10 to 12 hours.
6. The method for modifying delta-manganese dioxide as the positive electrode material of the copper ion-implanted zinc battery, according to claim 1, wherein the mass ratio of delta-manganese dioxide powder, the conductive agent and the binder in the second step is 14:4: 2.
7. The method for modifying delta-manganese dioxide as the positive electrode material of the copper ion implantation zinc battery as claimed in claim 1, wherein the volume ratio of the delta-manganese dioxide powder to the N-methyl pyrrolidone in the second step is 7mg:0.2 mL.
8. The method for modifying the positive electrode material delta-manganese dioxide of the copper ion implanted zinc battery according to claim 1, wherein the temperature of vacuum drying in the second step is 60-80 ℃; and in the second step, the current collector is a stainless steel net with the diameter of 12-14 mm.
9. The method for modifying the positive electrode material delta-manganese dioxide of the copper ion injection zinc battery according to claim 1, wherein the assembling of the water-based zinc ion battery by using the copper ion injection delta-manganese dioxide electrode sheet is completed by the following steps:
the battery can be directly assembled in the air, a zinc sheet is taken as a negative electrode, a manganese sulfate/zinc sulfate aqueous solution is taken as electrolyte, and the method comprises the following steps: assembling a 2025 button cell from top to bottom by the sequence of a positive electrode shell, a gasket, a delta-manganese dioxide electrode plate injected with copper ions, a diaphragm, a zinc plate and a negative electrode shell, dripping electrolyte to completely wet the positive electrode plate and the diaphragm, sealing by using a cell sealing machine, standing and activating to obtain the water-based zinc ion cell.
10. The method for modifying the copper ion-implanted zinc battery positive electrode material delta-manganese dioxide as claimed in claim 9, wherein the manganese sulfate/zinc sulfate aqueous solution is formed by mixing 0.1mol/L manganese sulfate aqueous solution and 2mol/L zinc sulfate aqueous solution according to a volume ratio of 1: 20; the activation time is 8-10 h.
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| CN114927632A (en) * | 2022-05-16 | 2022-08-19 | 湘潭大学 | Modified zinc metal sheet and preparation method and application thereof |
| CN114927632B (en) * | 2022-05-16 | 2024-01-26 | 湘潭大学 | Modified zinc metal sheet and preparation method and application thereof |
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