CN115472803B - 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 PDF

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CN115472803B
CN115472803B CN202211273295.0A CN202211273295A CN115472803B CN 115472803 B CN115472803 B CN 115472803B CN 202211273295 A CN202211273295 A CN 202211273295A CN 115472803 B CN115472803 B CN 115472803B
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周迎梅
韦正楠
魏麟骄
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New Energy Development Center Of Shengli Petroleum Administration Co Ltd Of Sinopec Group
Shandong Institute Of Petroleum And Chemical Engineering
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Abstract

The invention relates to the field of material preparation, in particular to a preparation method of a TMDs-based zinc ion battery anode material. The invention comprises the following steps: 1. preparation of SiO 2 A microsphere; 2. preparation of transition metal chalcogenide nanosheets coated SiO 2 Microsphere products; 3. preparing two-dimensional transition metal chalcogenide hollow microspheres; 4. and preparing the zinc ion battery anode material. According to the invention, the silicon dioxide microsphere is used as a sacrificial template to prepare the two-dimensional transition metal chalcogenide microsphere with a hollow structure, 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.

Description

Preparation method of TMDs-based zinc ion battery positive electrode material
Technical Field
The invention relates to the field of material preparation, in particular to a preparation method of a TMDs-based zinc ion battery anode material.
Background
With the development of social economy, the aggravation of energy crisis and the increasing increase of environmental pollution, people pay more attention to the development of green energy and the protection of ecological environment. Especially, as the PM2.5 index of part of cities in China is continuously increased in recent years and haze weather is frequent, the craving for fresh air and APEC blue is becoming increasingly strong. The development concept of full utilization of resources and energy and minimum environmental load advocated by the scientific community is deep, and the science and technology supporting the development concept is paid unprecedented attention. At present, the lithium ion battery is widely applied to small device equipment such as mobile phones, computers and the like by virtue of high energy density, long cycle life and the like. However, the content of lithium metal in the crust is low, the distribution is uneven, dendrites are extremely easy to generate in the charge and discharge process, a series of safety problems are caused, and the above factors severely restrict the application of the lithium ion battery in a large-scale energy storage system. The novel battery system with abundant development resources, low price, safety and reliability is the main melody developed in the current age. Compared with Li, the metal Zn has the advantages of high volume energy density, use of aqueous electrolyte (high safety), rich resource reserves (low cost) and the like. Therefore, the development of novel zinc ion batteries is one of the better choices of large-scale energy storage systems, and the research of extensive researchers is recently focused.
The energy storage mechanism of the zinc ion battery is similar to that of a lithium ion battery, and the zinc ion battery is based on the 'rocking chair' reversible reaction of alkali metal ions between the anode and the cathode. However, the high polarity of Zn < 2+ > causes the problems of blocked reversible deintercalation process, slow diffusion rate, material structure collapse in the cyclic charge and discharge process and the like in the positive electrode material, which severely restricts the commercialization process of the zinc ion battery. Therefore, how to design and prepare electrode materials with high energy density and long-time support of Zn2+ reversible deintercalation, especially positive electrode materials, is a key to solving the development bottleneck of rechargeable zinc batteries.
Compared with the traditional electrode material, the two-dimensional material has good stability, and has small deformation during ion embedding, thereby being beneficial to the rapid transfer of ions. Transition metal chalcogenides (TMDs) can be exfoliated into monolithic or less lamellar two-dimensional layered nanomaterials due to their weak van der waals forces from layer to layer. Within its monolayer, metal atoms are covalently bonded to chalcogen atoms, and layers are stacked together into a bulk material along the z-axis by weak van der Waals forces. The strong in-layer forces and the weak in-layer forces result in TMDs having a high degree of anisotropy and being easily exfoliated into single or few-lamellar nanoplatelet structures, thereby shortening the diffusion path of ions. When TMDs are exfoliated into single-or few-lamellar two-dimensional nanoplatelets, they exhibit some unique properties such as a large specific surface area, a special electronic structure, high reactivity, etc., in addition to maintaining the original excellent optical, electrical and mechanical properties due to the two-dimensional confinement effect of charges, and have higher thermal stability than metal oxides and contribute to oxygen-rich reduction reactions of high specific capacity, which makes them stand out from other materials as electrochemically active materials of energy storage devices. In addition, the ultrathin TMDs nano sheet can be self-assembled into various three-dimensional network structures, and is more beneficial to rapid transfer of electrons and transmission of ions, so that the effective utilization rate of TMDs active materials in electrochemical reaction is greatly improved. In addition, TMDs also have rich elemental compositions, and as metallic elements change, they exhibit a variety of electronic structural features that provide conditions for further tuning their intrinsic properties, providing a rich platform for obtaining high performance materials, and also providing convenience and possibilities for the design and performance optimization of high performance energy storage materials.
There are still problems associated with the current use of two-dimensional TMDs in the energy storage field. Firstly, most TMDs are semiconductors, and have poor conductivity, so that the application of TMDs in the field of energy storage is limited; secondly, most of two-dimensional TMDs are in sheet layers, so that agglomeration is easy to occur, and the capacity is low; the volume specific capacitance of the electrode material is proportional to the mass specific capacitance and the electrode bulk density; thirdly, the rate capability of the two-dimensional TMDs is poor in the case 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 as to further improve the performance of the material.
The invention adopts the following technical scheme: a preparation method of a TMDs-based zinc ion battery positive electrode material comprises the following steps:
s1: preparation of SiO 2 Microsphere(s)
S1.1: adding 10-20 parts by weight of ammonia water and 500-600 parts by weight of absolute ethyl alcohol into a reaction kettle, slowly adding 50-60 parts by weight of deionized water into the reaction kettle, stirring by a magnetic stirrer, and controlling the rotating speed at 150rpm to obtain a solution A;
s1.2: adding 20-40 parts by weight of ethyl orthosilicate into the solution A at a constant speed, and standing for 3-4 hours after the addition of 20-40 parts by weight of ethyl orthosilicate is completed to obtain a solution B;
s1.3: adding 50-60 parts by weight 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 centrifuging, 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 A microsphere;
s2: preparation of transition metal chalcogenide nanosheets coated SiO 2 Microsphere products;
s2.1: adding 100-120 parts by weight of transition metal chalcogenide nano-sheets into 200-300 parts by weight of ethylenediamine, and ultrasonically dispersing the transition metal chalcogenide nano-sheets into 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 by weight of SiO into the hydrothermal reaction kettle 2 The microsphere is subjected to hydrothermal reaction for 20-30h at the temperature of 150-200 ℃, and then cooled to room temperature to prepare emulsion A;
s2.3: vacuum-filtering 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 SiO coated by the transition metal chalcogenide nanosheets 2 Microsphere products;
s3: preparing two-dimensional transition metal chalcogenide hollow microspheres;
s3.1: coating SiO with transition metal chalcogenide nano-sheet 2 Adding the microsphere product into 200-300 parts by weight of 10% HF solution, raising the temperature to 50-70 ℃, and reacting for 3-4 hours to obtain a solid-liquid mixture A;
s3.2: filtering the solid-liquid mixture A, and then drying for 6-7 hours at 100-120 ℃ to obtain two-dimensional transition metal chalcogenide hollow microspheres;
s4: preparation of Zinc-ion cell cathode material
S4.1: mixing 40-50 parts by weight of two-dimensional transition metal chalcogenide hollow microspheres and 50-80 parts by weight 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 a water bath for 30-40min, and controlling the temperature to be 60-70 ℃ to obtain a solid product B;
s1.4.2: and (3) drying the solid product B at a high temperature for 1-2h, wherein the temperature is controlled at 150-170 ℃.
Further, the step S1.3 further includes the following steps:
s1.3.1: 5-8 parts by weight of 5.8mol/L HCl solution and 40-60 parts by weight of deionized water are added into the solution D, the solution D is centrifuged for 10-20min at 8000-9000rpm, the operation is repeated for 1 time, and the solution D is further treated.
Further comprises the following steps
S5: introduction of oxygen vacancies
S5.1: placing 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: 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 3-4h.
Further, the transition metal chalcogenide nanosheets are one or both of bismuth selenide nanosheets and bismuth telluride nanosheets.
Further, in the step S1.2, the solution a is controlled to be in a stirred state.
Further, the reducing gas is CO or NH 3 And H 2 One of them.
Further, in the step S4.1, the sintering forming temperature is controlled to be 1200-1500 ℃.
The invention has the following advantages:
1. according to the invention, the silicon dioxide microsphere is used as a sacrificial template to prepare the two-dimensional transition metal chalcogenide microsphere with a hollow structure, 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 invention carries out dilution elution on ammonia water through water washing and centrifugation; the ammonia water is further removed through acidification of the solution D by HCl, so that the stability of the silica microspheres is prevented from being influenced by the ammonia water.
3. According to the invention, the solution D is heated in a water bath and dried at a high temperature, so that the influence of one-time heating on the stability of the SiO2 microspheres is avoided, and in addition, the solution D can be uniformly heated by the water bath, so that the SiO2 microspheres are prevented from being heated unevenly;
4. according to the invention, the two-dimensional transition metal chalcogenide microspheres and the alpha-MnO 2 are compounded to prepare the zinc ion battery anode material, so that the excellent electrochemical performance of the alpha-MnO 2 is maintained;
5. according to the invention, the zinc ion battery anode material is treated by the reducing gas, lattice oxygen in the zinc ion battery anode material is abstracted, oxygen vacancies are introduced, so that oxygen defects in the zinc ion battery anode material are caused, the movement space of zinc ions in the zinc battery is further enlarged, and the electrochemical performance of the zinc battery is improved.
Drawings
Fig. 1 is a flowchart of a method for preparing a TMDs-based zinc ion battery cathode material according to an embodiment of the present invention.
Detailed Description
The invention will be further described with reference to specific embodiments for the purpose of making the objects, technical solutions and advantages of the invention more apparent, but the invention is not limited to these examples. It should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below. In the present invention, unless otherwise specified, all parts by weight and percentages are by mass, and the equipment, raw materials, etc. used are commercially available or are commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Examples
A preparation method of a TMDs-based zinc ion battery positive electrode material is shown in fig. 1, and comprises the following steps:
s1: preparation of SiO2 microspheres
S1.1: adding 10 parts by weight of ammonia water and 550 parts by weight of absolute ethyl alcohol into a reaction kettle, slowly adding 50 parts by weight of deionized water into the reaction kettle, and stirring by a magnetic stirrer at a rotating speed of 150rpm to obtain a solution A;
s1.2: adding 30 parts by weight of ethyl orthosilicate 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 addition of 30 parts by weight of ethyl orthosilicate is completed to obtain a solution B;
s1.3: adding 50 parts by weight of deionized water into the solution B, centrifuging for 10min at a rotating speed of 8000rpm to obtain a solution C, adding deionized water into the solution C to a volume before centrifuging, centrifuging for 10min at the rotating speed of 8000rpm, repeating the operation for 2 times to obtain a solution D, diluting and eluting ammonia water, and preventing the ammonia water from influencing the stability of silicon dioxide;
s1.3.1: adding 6 parts by weight of 5.8mol/L HCl solution and 50 parts by weight of deionized water into the solution D, further removing ammonia water through acidification of HCl to prevent the ammonia water from affecting the stability of the silica microspheres, centrifuging for 10min at a 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 a 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 a high temperature for 1h, wherein the temperature is controlled at 170 ℃;
s2: preparing a bismuth selenide nanosheet coated SiO2 microsphere product;
s2.1: adding 100 parts by weight of bismuth selenide nano-sheets into 280 parts by weight of ethylenediamine, and ultrasonically dispersing the bismuth selenide nano-sheets into ethylenediamine under the power of 20W to prepare bismuth selenide dispersion liquid;
s2.2: adding bismuth selenide dispersion liquid into a hydrothermal reaction kettle, adding 50 parts by weight of SiO2 microspheres into the hydrothermal reaction kettle, controlling the temperature to be 200 ℃, carrying out hydrothermal reaction for 24 hours, and as bismuth selenide is dispersed in ethylenediamine, enabling bismuth selenide nano-sheets to be uniformly coated on the SiO2 microspheres and then cooling to room temperature to prepare emulsion A;
s2.3: vacuum-filtering the emulsion A to obtain a solid product A, cleaning the solid product A by deionized water and absolute ethyl alcohol to remove redundant organic solvents, 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 a bismuth selenide nanosheet coated SiO2 microsphere product into 240 parts by weight of 10% HF solution, etching the SiO2 microsphere, removing the SiO2 microsphere to form a hollow structure of the bismuth selenide nanosheet, 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 the two-dimensional bismuth selenide hollow microspheres;
s4: preparation of Zinc-ion cell cathode material
S4.1: 40 parts by weight of two-dimensional transition metal chalcogenide hollow microspheres and 60 parts by weight of alpha-MnO 2 Mixing the powder, and then sintering and forming at 1200-1500 ℃ to prepare the zinc ion battery anode material;
s5: introduction of oxygen vacancies
S5.1: placing the zinc ion battery anode material into a reaction kettle, raising the temperature in the reaction kettle to 100 ℃, keeping the temperature for 15min,
s5.2: NH3 is introduced into the reaction kettle, the pressure is controlled to be 17MPa under the action of NH3, the temperature is raised to 700 ℃, and the reaction is continued for 4 hours under the heat preservation.
In the embodiment, due to the layered structure of bismuth selenide, good ion migration capability and proper interlayer spacing are provided, and excellent energy storage performance is achieved; the two-dimensional bismuth selenide microsphere with the hollow structure is arranged in the zinc ion battery anode material in the embodiment, the unique structure increases the active contact area of the active material and the electrolyte solution, reduces the transmission path of electrolyte ions in the active material system, and greatly improves the performance of the material.
Examples
A preparation method of a TMDs-based zinc ion battery positive electrode material is shown in fig. 1, and comprises the following steps:
s1: preparation of SiO2 microspheres
S1.1: adding 10 parts by weight of ammonia water and 550 parts by weight of absolute ethyl alcohol into a reaction kettle, slowly adding 50 parts by weight of deionized water into the reaction kettle, and stirring by a magnetic stirrer at a rotating speed of 150rpm to obtain a solution A;
s1.2: adding 30 parts by weight of ethyl orthosilicate 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 addition of 30 parts by weight of ethyl orthosilicate is completed to obtain a solution B;
s1.3: adding 50 parts by weight of deionized water into the solution B, centrifuging for 10min at a rotating speed of 8000rpm to obtain a solution C, adding deionized water into the solution C to a volume before centrifuging, centrifuging for 10min at the rotating speed of 8000rpm, repeating the operation for 2 times to obtain a solution D, diluting and eluting ammonia water, and preventing the ammonia water from influencing the stability of silicon dioxide;
s1.3.1: adding 6 parts by weight of 5.8mol/L HCl solution and 50 parts by weight of deionized water into the solution D, further removing ammonia water through acidification of HCl to prevent the ammonia water from affecting the stability of the silica microspheres, centrifuging for 10min at a 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 a 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 a high temperature for 1h, wherein the temperature is controlled at 170 ℃;
s2: preparing a bismuth telluride nanosheet coated SiO2 microsphere product;
s2.1: adding 100 parts by weight of bismuth telluride nano-sheets into 280 parts by weight of ethylenediamine, and ultrasonically dispersing the bismuth telluride nano-sheets into the ethylenediamine under the power of 20W to prepare bismuth telluride dispersion;
s2.2: adding bismuth telluride dispersion into a hydrothermal reaction kettle, adding 50 parts by weight of SiO2 microspheres into the hydrothermal reaction kettle, controlling the temperature to be 200 ℃, performing hydrothermal reaction for 24 hours, and as bismuth telluride is dispersed in ethylenediamine, enabling bismuth telluride nano-sheets to be uniformly coated on the SiO2 microspheres and then cooling to room temperature to prepare emulsion A;
s2.3: vacuum-filtering the emulsion A to obtain a solid product A, cleaning the solid product A by deionized water and absolute ethyl alcohol to remove redundant organic solvents, 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 a bismuth telluride nano sheet coated SiO2 microsphere product into 240 parts by weight of 10% HF solution, etching the SiO2 microsphere, removing the SiO2 microsphere to form a hollow structure of the bismuth telluride nano sheet, 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 telluride hollow microspheres;
s4: preparation of Zinc-ion cell cathode material
S4.1: mixing 40 parts by weight of two-dimensional transition metal chalcogenide hollow microspheres with 60 parts by weight of alpha-MnO 2 powder, and then sintering and forming at 1200-1500 ℃ to prepare a zinc ion battery anode material;
s5: introduction of oxygen vacancies
S5.1: placing the zinc ion battery anode material into a reaction kettle, raising the temperature in the reaction kettle to 100 ℃, keeping the temperature for 15min,
s5.2: NH3 is introduced into the reaction kettle, the pressure is controlled to be 17MPa under the action of NH3, the temperature is raised to 700 ℃, and the reaction is continued for 4 hours under the heat preservation.
In the embodiment, due to the special structure of bismuth telluride, reversible transmission of protons can be realized, and the energy storage performance of the positive electrode of the zinc ion battery 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 substance of the present invention are all within the scope of the technical solution of the present invention.

Claims (6)

1. The preparation method of the TMDs-based zinc ion battery positive electrode material is characterized by comprising the following steps of:
s1: preparation of SiO 2 Microsphere(s)
S1.1: adding 10-20 parts by weight of ammonia water and 500-600 parts by weight of absolute ethyl alcohol into a reaction kettle, slowly adding 50-60 parts by weight of deionized water into the reaction kettle, stirring by a magnetic stirrer, and controlling the rotating speed at 150rpm to obtain a solution A;
s1.2: adding 20-40 parts by weight of ethyl orthosilicate into the solution A at a constant speed, and standing for 3-4 hours after the addition of 20-40 parts by weight of ethyl orthosilicate is completed to obtain a solution B;
s1.3: adding 50-60 parts by weight 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 centrifuging, 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 A microsphere;
s2: preparation of transition metal chalcogenide nanosheets coated SiO 2 Microsphere products;
s2.1: adding 100-120 parts by weight of transition metal chalcogenide nano-sheets into 200-300 parts by weight of ethylenediamine, and ultrasonically dispersing the transition metal chalcogenide nano-sheets into 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 by weight of SiO into the hydrothermal reaction kettle 2 The microsphere is subjected to hydrothermal reaction for 20-30h at the temperature of 150-200 ℃, and then cooled to room temperature to prepare emulsion A;
s2.3: vacuum-filtering 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 SiO coated by the transition metal chalcogenide nanosheets 2 Microsphere products;
s3: preparing two-dimensional transition metal chalcogenide hollow microspheres;
s3.1: coating SiO with transition metal chalcogenide nano-sheet 2 Adding the microsphere product into 200-300 parts by weight of 10% HF solution, raising the temperature to 50-70 ℃, and reacting for 3-4 hours to obtain a solid-liquid mixture A;
s3.2: filtering the solid-liquid mixture A, and then drying for 6-7 hours at 100-120 ℃ to obtain two-dimensional transition metal chalcogenide hollow microspheres;
s4: preparation of Zinc-ion cell cathode material
S4.1: 40 to 50 weight parts of two-dimensional transition metal chalcogenide hollow microspheres and 50 to 80 weight parts of alpha-MnO 2 Mixing the powder, and then sintering and forming to obtain the zinc ion battery anode material;
the transition metal chalcogenide nanosheets are one or two of bismuth selenide nanosheets and bismuth telluride nanosheets;
in the step S4.1, the sintering forming temperature is controlled between 1200 ℃ and 1500 ℃.
2. The method for preparing the cathode material of the zinc ion battery based on TMDs according to claim 1, wherein the step S1.4 specifically comprises 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 a water bath for 30-40min, and controlling the temperature to be 60-70 ℃ to obtain a solid product B;
s1.4.2: and (3) drying the solid product B at a high temperature for 1-2h, wherein the temperature is controlled at 150-170 ℃.
3. The method for preparing a TMDs-based zinc ion battery cathode material according to claim 1, wherein the step S1.3 further comprises the steps of:
s1.3.1: 5-8 parts by weight of 5.8mol/L HCl solution and 40-60 parts by weight of deionized water are added into the solution D, the solution D is centrifuged for 10-20min at 8000-9000rpm, the operation is repeated for 1 time, and the solution D is further treated.
4. The method for preparing the TMDs-based zinc ion battery positive electrode material according to claim 1, further comprising the following steps
S5: introduction of oxygen vacancies
S5.1: placing 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: 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 3-4h.
5. The method for preparing a cathode material for zinc-ion batteries based on TMDs according to claim 1, wherein in the step S1.2, the solution a is controlled to be in a stirred state.
6. The method for preparing a TMDs-based zinc-ion battery cathode material according to claim 4, wherein the reducing gas is CO or NH 3 And H 2 One of them.
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Publication number Priority date Publication date Assignee Title
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