CN115472803A - Preparation method of TMDS-based zinc ion battery positive electrode material - Google Patents
Preparation method of TMDS-based zinc ion battery positive electrode material Download PDFInfo
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Abstract
The invention relates to the field of material preparation, in particular to a TMDs-based preparation method of a zinc ion battery positive electrode material. The invention comprises the following steps: 1. preparation of SiO 2 Microspheres; 2. preparation of transition metal chalcogenide nanosheet coated SiO 2 A microsphere product; 3. preparing two-dimensional transition metal chalcogenide hollow microspheres; 4. preparing the positive electrode material of the zinc ion battery. The invention prepares the composite material by taking silicon dioxide microspheres as sacrificial templatesThe unique structure of the two-dimensional transition metal chalcogenide microsphere with a hollow structure increases the active contact area of an active material and an electrolyte solution, reduces the transmission path of electrolyte ions in an active material system, and greatly improves the performance of the material.
Description
The technical field is as follows:
the invention relates to the field of material preparation, in particular to a TMDs-based preparation method of a zinc ion battery positive electrode material.
Background art:
with the development of social economy, the aggravation of energy crisis and the increasing aggravation of environmental pollution, people pay more and more attention to the development of green energy and the protection of ecological environment. Particularly, along with the increasing PM2.5 index of partial cities in China and frequent haze weather in recent years, people have increasingly strong desire for fresh air and APEC blue. The development concept of full utilization of resources and energy and minimum environmental load advocated by the scientific community is deeply focused, and the scientific technology supporting the development concept is paid unprecedented attention. At present, lithium ion batteries are widely applied to small devices such as mobile phones and computers due to the advantages of high energy density, long cycle life and the like. However, the content of lithium metal in the earth crust is low, the distribution is not uniform, and dendrites are easily generated in the charging and discharging process, so that a series of safety problems are caused, and the application of the lithium ion battery in a large energy storage system is severely restricted by the above factors. The development resource is rich, the price is cheap, the safe and reliable new battery system is the main melody that the modern times develop. Compared with Li, metal Zn has the advantages of high volume energy density, high safety of using aqueous electrolyte, rich resource reserves (low cost) and the like. Therefore, the great development of a novel zinc ion battery is one of the better choices of a large-scale energy storage system, and the zinc ion battery is closely concerned by a large number of researchers in recent years.
The energy storage mechanism of zinc ion batteries is similar to that of lithium ion batteries, and is based on the rocking chair type reversible reaction of alkali metal ions between a positive electrode and a negative electrode. However, the Zn < 2+ > has high polarity, so that the reversible de-intercalation process of the Zn < 2+ > in the cathode material is blocked, the diffusion rate is slow, the material structure collapses in the cyclic charge and discharge process and the like, and the commercialization process of the zinc ion battery is severely restricted. Therefore, how to design and prepare an electrode material which has high energy density and can support reversible extraction of Zn & lt 2+ & gt for a long time, particularly a positive electrode material is a key for solving the development bottleneck of a rechargeable zinc battery.
Compared with the traditional electrode material, the two-dimensional material has good stability, has small deformation when ions are embedded, and is beneficial to the rapid transfer of the ions. Transition metal chalcogenides (TMDs) can be exfoliated into monolithic or lamellar-less two-dimensional layered nanomaterials due to the weaker van der waals forces between layers. Within its monolayer, metal atoms are covalently bonded to chalcogen atoms, and the layers are stacked in the z-axis direction by weak van der waals forces between layers. Strong intralayer forces and weak interlayer forces cause TMDs to have high anisotropy and at the same time be easily exfoliated into monolayer or few-lamellar nanosheet structures, thereby shortening the diffusion path of ions. When TMDs are stripped into single-layer or few-layer two-dimensional nanosheets, due to the two-dimensional confinement effect of charges, the TMDs also show some unique properties such as large specific surface area, special electronic structure, high reactivity and the like, and oxygen-enriched redox reaction which has higher thermal stability and is beneficial to high specific capacity than metal oxide, besides maintaining the original excellent optical, electrical and mechanical properties, so that the TMDs are distinguished from other materials as electrochemical active materials of energy storage devices. In addition, the ultrathin TMDS nanosheets can be self-assembled into various three-dimensional network structures, which is more favorable for the rapid transfer of electrons and the transmission of ions, thereby greatly improving the effective utilization rate of TMDS active materials in electrochemical reaction. In addition, TMDs also have abundant elemental compositions, and as metallic elements change, they exhibit a wide variety of electronic structural features, which provide conditions for further regulating their intrinsic physical properties, provide a rich platform for obtaining high-performance materials, and provide convenience and possibility for the design and performance optimization of high-performance energy storage materials.
The current application of two-dimensional TMDs in the field of energy storage still has some problems. Firstly, most TMDs are semiconductors, and the conductivity is poor, so that the application of the TMDs in the field of energy storage is limited; secondly, the two-dimensional TMDs mostly have the problems that the sheet layers are easy to agglomerate and have low capacity; the volume specific capacitance of the electrode material is in direct proportion to the mass specific capacitance and the electrode packing density; thirdly, the rate performance of the two-dimensional TMDs is not good under the condition of large-current discharge.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a TMDs-based zinc ion battery anode material, which is used for preparing two-dimensional transition metal chalcogenide hollow microspheres by a sacrificial template method, so that the performance of the material is further improved.
The invention adopts the following technical scheme: a preparation method of a TMDS-based positive electrode material of a zinc ion battery comprises the following steps:
s1: preparation of SiO 2 Microspheres
S1.1: adding 10-20 parts of ammonia water and 500-600 parts of absolute ethyl alcohol into a reaction kettle, slowly adding 50-60 parts of deionized water into the reaction kettle, and stirring by a magnetic stirrer at the rotating speed of 150rpm to obtain a solution A;
s1.2: adding 20-40 parts of tetraethoxysilane into the solution A at a constant speed, and standing for 3-4 hours after the 20-40 parts of tetraethoxysilane are added to obtain a solution B;
s1.3: adding 50-60 parts of deionized water into the solution B, centrifuging at 8000-9000rpm for 10-20min to obtain solution C, adding deionized water into the solution C to the volume before centrifugation, centrifuging at 8000-9000rpm for 10-20min, and repeating the operation for 2 times to obtain solution D;
s1.4: drying the solution D to obtain SiO 2 Microspheres;
s2: preparation of transition metal chalcogenide nanosheet coated SiO 2 A microsphere product;
s2.1: adding 100-120 parts of transition metal chalcogenide nanosheets into 200-300 parts of ethylenediamine, and ultrasonically dispersing the transition metal chalcogenide nanosheets into the ethylenediamine under the power of 20W to prepare a transition metal chalcogenide dispersion liquid;
s2.2: adding the transition metal chalcogenide dispersion liquid into a hydrothermal reaction kettle, and adding the transition metal chalcogenide dispersion liquid into the hydrothermal reaction kettle50-60 parts of SiO 2 Carrying out hydrothermal reaction on microspheres for 20-30h at the temperature of 150-200 ℃, and then cooling to room temperature to prepare emulsion A;
s2.3: carrying out vacuum filtration on the emulsion A to obtain a solid product A, cleaning the solid product A by deionized water and absolute ethyl alcohol, and then annealing the solid product A in an argon atmosphere to obtain the transition metal chalcogenide nanosheet-coated SiO 2 A microsphere product;
s3: preparing two-dimensional transition metal chalcogenide hollow microspheres;
s3.1: siO coating transition metal chalcogenide nanosheets 2 Adding the microsphere product into 200-300 parts of 10% HF solution, heating to 50-70 deg.C, and reacting for 3-4 hr to obtain solid-liquid mixture A;
s3.2: filtering the solid-liquid mixture A, and then drying for 6-7h at the temperature of 100-120 ℃ to obtain two-dimensional transition metal chalcogenide hollow microspheres;
s4: preparation of positive electrode material of zinc ion battery
S4.1: mixing 40-50 parts of two-dimensional transition metal chalcogenide hollow microspheres and 50-80 parts of alpha-MnO 2 powder, and then sintering and forming to obtain the zinc ion battery anode material.
Further, the step S1.4 specifically includes the following steps:
s1.4.1: placing the solution D in a container, stirring the solution D clockwise by a stirrer, heating the solution D in water bath for 30-40min, and controlling the temperature to be 60-70 ℃ to obtain a solid product B;
s1.4.2: drying the solid product B at high temperature for 1-2h, and controlling the temperature at 150-170 ℃.
Further, the step S1.3 further comprises the steps of:
s1.3.1: and 5-8 parts of 5.8mol/L HCl solution and 40-60 parts of deionized water are added into the solution D, the solution D is centrifuged for 10-20min at the rotating speed of 8000-9000rpm, the operation is repeated for 1 time, and the solution D is further processed.
Further, the method also comprises the following steps
S5: introduction of oxygen vacancies
S5.1: putting the zinc ion battery anode material into a reaction kettle, raising the temperature in the reaction kettle to 100-110 ℃, keeping the temperature for 10-20min,
s5.2: and introducing reducing gas into the reaction kettle, controlling the pressure to be 15-17MPa, raising the temperature to 500-700 ℃, and keeping the temperature for continuous reaction for 3-4 hours.
Further, the transition metal chalcogenide nanosheets are one or two of bismuth selenide nanosheets and bismuth telluride nanosheets.
Further, in step S1.2, solution a is controlled to be in a stirred state.
Further, the reducing gas is CO or NH 3 And H 2 One kind of (1).
Further, in the step S4.1, the temperature of sintering and forming is controlled to be 1200-1500 ℃.
The invention has the following advantages:
1. the invention prepares the two-dimensional transition metal chalcogenide microsphere with a hollow structure by taking the silicon dioxide microsphere as a sacrificial template, and the unique structure of the two-dimensional transition metal chalcogenide microsphere increases the active contact area of an active material and an electrolyte solution, reduces the transmission path of electrolyte ions in an active material system, and greatly improves the performance of the material.
2. The ammonia water is diluted and eluted by water washing and centrifugation; and acidifying the solution D by HCl to further remove ammonia water, so that the ammonia water is prevented from influencing the stability of the silicon dioxide microspheres.
3. According to the invention, the solution D is subjected to water bath heating and high-temperature drying, so that the influence of one-time temperature rise on the stability of the SiO2 microspheres is avoided, and in addition, the solution D can be uniformly heated by the water bath heating, so that the SiO2 microspheres are prevented from being heated unevenly;
4. according to the invention, the zinc ion battery anode material is prepared by compounding the two-dimensional transition metal chalcogenide microspheres and the alpha-MnO 2, and the excellent electrochemical performance of the alpha-MnO 2 is reserved;
5. according to the invention, the reducing gas is used for treating the zinc ion battery anode material, so that the lattice oxygen in the zinc ion battery anode material is captured, and the oxygen vacancy is introduced, so that the oxygen defect in the zinc ion battery anode material is caused, the movement space of zinc ions in the zinc battery is further expanded, and the electrochemical performance of the zinc battery is improved.
Drawings
Fig. 1 is a flowchart of a method for preparing a TMDs-based positive electrode material for a zinc-ion battery according to an embodiment of the present invention.
The specific implementation mode is as follows:
the present invention will be further described with reference to specific embodiments for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, but the present invention is not limited to these examples. It should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment. In the invention, all parts and percentages are mass units, and the adopted equipment, raw materials and the like are commercially available or commonly used in the field. The methods in the following examples are all conventional in the art unless otherwise specified.
Example 1
A preparation method of a TMDS-based positive electrode material of a zinc ion battery is shown in figure 1 and comprises the following steps:
s1: preparation of SiO2 microspheres
S1.1: adding 10 parts of ammonia water and 550 parts of absolute ethyl alcohol into a reaction kettle, slowly adding 50 parts of deionized water into the reaction kettle, and stirring by a magnetic stirrer, wherein the rotating speed is controlled at 150rpm to obtain a solution A;
s1.2: adding 30 parts of tetraethoxysilane into the solution A at a constant speed, controlling the solution A to be in a stirred state, and standing for 3 hours after the 30 parts of tetraethoxysilane are added to obtain a solution B;
s1.3: adding 50 parts of deionized water into the solution B, centrifuging at the rotating speed of 8000rpm for 10min to obtain a solution C, adding deionized water into the solution C to the volume before centrifuging, centrifuging at the rotating speed of 8000rpm for 10min, repeating the operation for 2 times to obtain a solution D, diluting and eluting ammonia water, and preventing the ammonia water from affecting the stability of silicon dioxide;
s1.3.1: adding 6 parts of 5.8mol/L HCl solution and 50 parts of deionized water into the solution D, acidifying the solution D through HCl, further removing ammonia water, preventing the ammonia water from influencing the stability of the silicon dioxide microspheres, centrifuging the solution D for 10min at the rotating speed of 8000rpm, repeating the operation for 1 time, and further treating the solution D;
s1.4.1: putting the solution D into a container, stirring the solution D clockwise by a stirrer, heating the solution D in water bath for 30min, and controlling the temperature to be 60 ℃ to obtain a solid product B;
s1.4.2: drying the solid product B at high temperature for 1h, and controlling the temperature at 170 ℃;
s2: preparing a bismuth selenide nanosheet coated SiO2 microsphere product;
s2.1: adding 100 parts of bismuth selenide nanosheets into 280 parts of ethylenediamine, and ultrasonically dispersing the bismuth selenide nanosheets into the ethylenediamine under the power of 20W to prepare bismuth selenide dispersion liquid;
s2.2: adding the bismuth selenide dispersion liquid into a hydrothermal reaction kettle, adding 50 parts of SiO2 microspheres into the hydrothermal reaction kettle, controlling the temperature at 200 ℃, carrying out hydrothermal reaction for 24 hours, uniformly coating bismuth selenide nanosheets on the SiO2 microspheres due to the dispersion of bismuth selenide in ethylenediamine, and then cooling to room temperature to obtain emulsion A;
s2.3: carrying out vacuum filtration on the emulsion A to obtain a solid product A, washing the solid product A by deionized water and absolute ethyl alcohol, washing away redundant organic solvent, and then annealing the solid product A in an argon atmosphere to obtain a bismuth selenide nanosheet coated SiO2 microsphere product;
s3: preparing two-dimensional bismuth selenide hollow microspheres;
s3.1: adding the product of the bismuth selenide nanosheet-coated SiO2 microspheres into 240 parts of 10% HF solution, etching the SiO2 microspheres, removing the SiO2 microspheres to enable the bismuth selenide nanosheet to form a hollow structure, raising the temperature to 50 ℃, and reacting for 3 hours to obtain a solid-liquid mixture A;
s3.2: filtering the solid-liquid mixture A, and then drying for 7 hours at 120 ℃ to obtain two-dimensional bismuth selenide hollow microspheres;
s4: preparation of positive electrode material of zinc ion battery
S4.1: 40 parts of two-dimensional transition metal chalcogenide hollow microspheres and 60 parts of alpha-MnO 2 Mixing the powder, and then sintering and molding at 1200-1500 ℃ to obtain the zinc ion battery anode material;
s5: introduction of oxygen vacancies
S5.1: putting the positive electrode material of the zinc ion battery into a reaction kettle, raising the temperature in the reaction kettle to 100 ℃, keeping the temperature for 15min,
s5.2: introducing NH3 into the reaction kettle, controlling the pressure to be 17MPa under the action of the NH3, raising the temperature to 700 ℃, and keeping the temperature for continuous reaction for 4 hours.
In the embodiment, due to the layered structure of the bismuth selenide, good ion migration capability and appropriate interlayer spacing are provided, and the bismuth selenide has excellent energy storage performance; the zinc ion battery positive electrode material in the embodiment is provided with the two-dimensional bismuth selenide microspheres with the hollow structures, the unique structure of the two-dimensional bismuth selenide microspheres increases the active contact area of the active material and the electrolyte solution, reduces the transmission path of electrolyte ions in an active material system, and greatly improves the performance of the material.
Example 2
A preparation method of a TMDS-based positive electrode material of a zinc ion battery is shown in figure 1 and comprises the following steps:
s1: preparation of SiO2 microspheres
S1.1: adding 10 parts of ammonia water and 550 parts of absolute ethyl alcohol into a reaction kettle, slowly adding 50 parts of deionized water into the reaction kettle, and stirring by using a magnetic stirrer, wherein the rotating speed is controlled at 150rpm, so as to obtain a solution A;
s1.2: adding 30 parts of tetraethoxysilane into the solution A at a constant speed, controlling the solution A to be in a stirred state, and standing for 3 hours after the 30 parts of tetraethoxysilane are added to obtain a solution B;
s1.3: adding 50 parts of deionized water into the solution B, centrifuging at the rotating speed of 8000rpm for 10min to obtain a solution C, adding deionized water into the solution C to the volume before centrifugation, centrifuging at the rotating speed of 8000rpm for 10min, repeating the operation for 2 times to obtain a solution D, diluting and eluting ammonia water, and preventing the ammonia water from affecting the stability of silicon dioxide;
s1.3.1: adding 6 parts of 5.8mol/L HCl solution and 50 parts of deionized water into the solution D, acidifying the solution D through HCl, further removing ammonia water, preventing the ammonia water from influencing the stability of the silicon dioxide microspheres, centrifuging the solution D for 10min at the rotating speed of 8000rpm, repeating the operation for 1 time, and further treating the solution D;
s1.4.1: placing the solution D in a container, stirring the solution D clockwise by a stirrer, heating the solution D in water bath for 30min, and controlling the temperature to be 60 ℃ to obtain a solid product B;
s1.4.2: drying the solid product B at high temperature for 1h, and controlling the temperature at 170 ℃;
s2: preparing a bismuth telluride nanosheet coated SiO2 microsphere product;
s2.1: adding 100 parts of bismuth telluride nanosheets into 280 parts of ethylenediamine, and ultrasonically dispersing the bismuth telluride nanosheets into the ethylenediamine under the power of 20W to prepare bismuth telluride dispersion liquid;
s2.2: adding the bismuth telluride dispersion liquid into a hydrothermal reaction kettle, adding 50 parts of SiO2 microspheres into the hydrothermal reaction kettle, controlling the temperature at 200 ℃, carrying out hydrothermal reaction for 24 hours, uniformly coating bismuth telluride nanosheets on the SiO2 microspheres due to the dispersion of bismuth telluride in ethylenediamine, and cooling to room temperature to obtain emulsion A;
s2.3: carrying out vacuum filtration on the emulsion A to obtain a solid product A, washing the solid product A by deionized water and absolute ethyl alcohol, washing away redundant organic solvent, and then annealing the solid product A in an argon atmosphere to obtain a bismuth telluride nanosheet-coated SiO2 microsphere product;
s3: preparing two-dimensional bismuth telluride hollow microspheres;
s3.1: adding the product of coating the bismuth telluride nano-sheet with the SiO2 microspheres into 240 parts of 10 percent HF solution, etching the SiO2 microspheres, removing the SiO2 microspheres to enable the bismuth telluride nano-sheet to form a hollow structure, raising the temperature to 50 ℃, and reacting for 3 hours to obtain a solid-liquid mixture A;
s3.2: filtering the solid-liquid mixture A, and then drying for 7h at 120 ℃ to obtain two-dimensional bismuth telluride hollow microspheres;
s4: preparation of positive electrode material of zinc ion battery
S4.1: mixing 40 parts of two-dimensional transition metal chalcogenide hollow microspheres and 60 parts of alpha-MnO 2 powder, and sintering at 1200-1500 ℃ to obtain a zinc ion battery anode material;
s5: introduction of oxygen vacancies
S5.1: putting the positive electrode material of the zinc ion battery into a reaction kettle, raising the temperature in the reaction kettle to 100 ℃, keeping the temperature for 15min,
s5.2: and (3) introducing NH3 into the reaction kettle, controlling the pressure to be 17MPa under the action of the NH3, raising the temperature to 700 ℃, and keeping the temperature for continuous reaction for 4 hours.
In the embodiment, due to the special structure of the bismuth telluride, the proton can be reversibly transmitted, and the energy storage performance of the zinc ion battery anode is improved.
The above embodiments are merely preferred embodiments of the present invention, and any simple modification, modification and substitution changes made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (8)
1. A preparation method of a TMDs-based zinc ion battery positive electrode material is characterized by comprising the following steps:
s1: preparation of SiO 2 Microspheres
S1.1: adding 10-20 parts of ammonia water and 500-600 parts of absolute ethyl alcohol into a reaction kettle, slowly adding 50-60 parts of deionized water into the reaction kettle, and stirring by using a magnetic stirrer, wherein the rotating speed is controlled at 150rpm, so as to obtain a solution A;
s1.2: adding 20-40 parts of tetraethoxysilane into the solution A at a constant speed, and standing for 3-4 hours after the 20-40 parts of tetraethoxysilane are added to obtain a solution B;
s1.3: adding 50-60 parts of deionized water into the solution B, centrifuging at 8000-9000rpm for 10-20min to obtain solution C, adding deionized water into the solution C to the volume before centrifugation, centrifuging at 8000-9000rpm for 10-20min, and repeating the operation for 2 times to obtain solution D;
s1.4: mixing the solutionD, drying to obtain SiO 2 Microspheres;
s2: preparation of transition metal chalcogenide nanosheet-coated SiO 2 A microsphere product;
s2.1: adding 100-120 parts of transition metal chalcogenide nanosheets into 200-300 parts of ethylenediamine, and ultrasonically dispersing the transition metal chalcogenide nanosheets into the ethylenediamine under the power of 20W to prepare a transition metal chalcogenide dispersion liquid;
s2.2: adding the transition metal chalcogenide dispersion liquid into a hydrothermal reaction kettle, and adding 50-60 parts of SiO into the hydrothermal reaction kettle 2 Carrying out hydrothermal reaction on microspheres for 20-30h at the temperature of 150-200 ℃, and then cooling to room temperature to prepare emulsion A;
s2.3: carrying out vacuum filtration on the emulsion A to obtain a solid product A, cleaning the solid product A by deionized water and absolute ethyl alcohol, and then annealing the solid product A in an argon atmosphere to obtain a transition metal chalcogenide nanosheet-coated SiO 2 A microsphere product;
s3: preparing two-dimensional transition metal chalcogenide hollow microspheres;
s3.1: siO coating transition metal chalcogenide nanosheets 2 Adding the microsphere product into 200-300 parts of 10% HF solution, heating to 50-70 deg.C, and reacting for 3-4 hr to obtain solid-liquid mixture A;
s3.2: filtering the solid-liquid mixture A, and then drying for 6-7h at the temperature of 100-120 ℃ to obtain two-dimensional transition metal chalcogenide hollow microspheres;
s4: preparation of positive electrode material of zinc ion battery
S4.1: 40-50 parts of two-dimensional transition metal chalcogenide hollow microspheres and 50-80 parts of alpha-MnO 2 And mixing the powder, and then sintering and forming to obtain the zinc ion battery anode material.
2. The method for preparing the TMDS-based zinc-ion battery positive electrode material according to claim 1, wherein the step S1.4 specifically comprises the following steps:
s1.4.1: putting the solution D into a container, stirring the solution D clockwise by a stirrer, heating the solution D in water bath for 30-40min, and controlling the temperature to be 60-70 ℃ to obtain a solid product B;
s1.4.2: drying the solid product B at high temperature for 1-2h, and controlling the temperature at 150-170 ℃.
3. The method for preparing the TMDS-based positive electrode material of the zinc-ion battery according to claim 1, wherein the step S1.3 further comprises the following steps:
s1.3.1: 5-8 parts of 5.8mol/L HCl solution and 40-60 parts of deionized water are added into the solution D, and the solution D is further processed by centrifuging for 10-20min at the rotating speed of 8000-9000rpm, repeating the operation for 1 time.
4. The method for preparing the positive electrode material of the TMDS-based zinc-ion battery according to claim 1, further comprising the following steps
S5: introduction of oxygen vacancies
S5.1: putting the zinc ion battery anode material into a reaction kettle, raising the temperature in the reaction kettle to 100-110 ℃, keeping the temperature for 10-20min,
s5.2: and introducing reducing gas into the reaction kettle, controlling the pressure to be 15-17MPa, raising the temperature to 500-700 ℃, and keeping the temperature for continuous reaction for 3-4 hours.
5. The preparation method of the TMDs-based zinc-ion battery cathode material according to claim 1, wherein the transition metal chalcogenide nanosheets are one or both of bismuth selenide nanosheets and bismuth telluride nanosheets.
6. The method according to claim 1, wherein in step S1.2, solution A is controlled to be in a stirred state.
7. The preparation method of the TMDS-based positive electrode material for the zinc-ion battery according to claim 4, wherein the TMDS-based positive electrode material is prepared by a method comprisingThen, the reducing gas is CO, NH 3 And H 2 One kind of (1).
8. The method for preparing the positive electrode material of the TMDs-based zinc-ion battery according to claim 1, wherein the sintering temperature in step S4.1 is controlled to be 1200-1500 ℃.
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