CN-118458798-B - Preparation method of octacyanogen manganese molybdate nanoparticle/carbon nanotube composite material and application of octacyanogen manganese molybdate nanoparticle/carbon nanotube composite material to positive electrode of water-based zinc ion battery

Abstract

The invention belongs to the technical field of composite materials, and relates to an electrode material, in particular to a preparation method of an octacyanomanganese molybdate nanoparticle/carbon nanotube (Mn 2 [Mo(CN) 8 /CNTs) composite material, which comprises the steps of preparing carboxylated carbon nanotube dispersion liquid and manganese salt aqueous solution, and mixing the carboxylated carbon nanotube dispersion liquid and the manganese salt aqueous solution; and adding the prepared potassium octacyanomolybdate aqueous solution, stirring uniformly, adding isopropanol, standing, centrifugally separating, washing with deionized water and ethanol, and vacuum drying. The Mn 2 [Mo(CN) 8 nano particle and carbon nano tube composite material is prepared by a coprecipitation method, the octacyanomolybdic acid manganese nano particle grows on the surface of the carbon nano tube conductive framework in situ, and the prepared composite material is also applied to the anode of the water system zinc ion battery. The preparation method is simple and feasible in operation, good in composite effect, and the prepared composite material shows excellent zinc storage performance, is suitable for large-scale production, and has potential application prospect.

Inventors

• SHEN XIAOPING
• Pu Jinrui
• JI ZHENYUAN

Assignees

• 江苏大学

Dates

Publication Date

20260512

Application Date

20240430

Claims (9)

1. 1. The preparation method of the octacyanogen manganese molybdate nanoparticle/carbon nanotube composite material is characterized by comprising the following steps of: (1) Stirring and ultrasonically dispersing the carboxylated multiwall carbon nanotubes in deionized water to obtain a carbon nanotube dispersion liquid, namely a solution A, wherein the mass volume ratio of the carbon nanotubes to the deionized water is 5-40 mg/5-40 mL; (2) Dissolving a manganese source in deionized water, namely a solution B, wherein the molar ratio of the manganese source to the deionized water is 0.5-2 mmol to 5-20 mL, and the manganese source is manganese chloride, manganese sulfate, manganese acetate or manganese nitrate; (3) Preparing deionized water solution of potassium octacyanomolybdate, namely solution C, wherein the mass volume ratio of the potassium octacyanomolybdate to the deionized water is 115-460 mg/10-30 mL; (4) Adding the solution C into the mixed solution obtained in the step (2) according to the volume ratio of 2:3, adding isopropanol, wherein the volume ratio of the isopropanol to the solution C is 2.5-7.5 mL:10-30 mL, standing for 3 days, centrifugally separating the obtained precipitate, washing with deionized water and ethanol, and vacuum drying at 60 ℃ to obtain the manganese octacyanomolybdate nano-particle/carbon nano-tube composite material.
2. 2. The method for preparing the manganese octacyanomolybdate nanoparticle/carbon nanotube composite material according to claim 1, wherein in the step (1), the mass-to-volume ratio of the carbon nanotubes to deionized water is 20 mg/20 mL.
3. 3. The method for preparing a manganese octacyanomolybdate nanoparticle/carbon nanotube composite material according to claim 1, wherein in the step (2), the molar ratio of the manganese source to deionized water is 1 mmol/10 mL.
4. 4. The method for preparing a manganese octacyanomolybdate nanoparticle/carbon nanotube composite material according to claim 1, wherein in the step (2), the manganese source is manganese chloride.
5. 5. The method for preparing the manganese octacyanomolybdate nanoparticle/carbon nanotube composite material according to claim 1, wherein in the step (3), the mass-volume ratio of potassium octacyanomolybdate to deionized water is 230 mg/20 mL.
6. 6. The method of claim 1, wherein in the step (4), the volume ratio of the isopropyl alcohol to the solution C is 5 mL/20 mL.
7. 7. The manganese octacyanomolybdate nanoparticle/carbon nanotube composite material prepared by the method according to any one of claims 1-6.
8. 8. The manganese octacyanomolybdate nanoparticle/carbon nanotube composite material of claim 7, wherein the Mn 2 [Mo(CN) 8 nanoparticle has a size of 30+ -10 nm and is attached to the surface of the carbon nanotube conductive backbone.
9. 9. The application of the octacyanomanganese molybdate nanoparticle/carbon nanotube composite material according to claim 7 or 8, which is characterized in that the octacyanomanganese molybdate nanoparticle/carbon nanotube composite material is applied to an aqueous zinc ion battery anode material.

Description

Preparation method of octacyanogen manganese molybdate nanoparticle/carbon nanotube composite material and application of octacyanogen manganese molybdate nanoparticle/carbon nanotube composite material to positive electrode of water-based zinc ion battery Technical Field The invention belongs to the technical field of composite materials, relates to a nanocomposite material, and in particular relates to a preparation method of an octacyanomanganese molybdate nanoparticle/carbon nanotube (Mn 2[Mo(CN)8/CNTs) composite material and application thereof to an anode of a water-based zinc ion battery. Technical Field With the rapid development of socioeconomic performance, the reserves of traditional fossil fuels are becoming smaller and smaller, and the demand of energy is increasing. New renewable energy sources such as solar energy, hydropower, tidal energy, geothermal energy, wind energy and the like need to be developed. Therefore, large-scale stationary energy storage systems must be developed to ensure distribution and supply of power. Rechargeable batteries are considered the most promising energy storage devices because of their high efficiency and durability. Lithium ion batteries are outstanding in the energy storage field by virtue of their high energy density and excellent cycle performance. However, in view of the poor safety and high cost of lithium ion batteries, there is a need to explore a safe, environmentally friendly, low cost alternative battery system. Recently, aqueous zinc ion batteries have gained favor of researchers as an emerging secondary battery, and the stability of metallic Zn in aqueous electrolyte and the appropriate electrode potential (-0.762V vs SHE) make it possible to directly serve as the negative electrode of aqueous zinc ion batteries. In addition, the metal Zn has the advantages of high theoretical capacity (5854 mAh cm -3 and 820mAh g -1), rich reserves and low price. Many advantages make the water system zinc ion battery hopeful to become the first choice of large-scale energy storage system in future. One of the main reasons for impeding the large-scale application of the water-based zinc ion battery at present is the lack of a proper positive electrode material, so the exploration of a novel high-efficiency positive electrode material has important significance for the development of the water-based zinc ion battery. Prussian Blue Analogues (PBAs) with three-dimensional open frame structure have attracted extensive attention from researchers due to their advantages of adjustable composition, simple synthesis, etc. However, PBAs has problems such as low specific capacity and poor cycle stability as the positive electrode of the aqueous zinc ion battery. The electrochemical energy storage properties of PBAs can be attributed to the redox behavior of the transition metal ions, by which the energy storage properties of PBAs can be tuned. In addition, the current PBAs positive electrode materials mainly focus on the research of a first transition metal, and a second transition metal is not yet involved. The metal octacyanomolybdenum compound and PBAs belong to cyano-bridged three-dimensional structure compounds, but the framework crystal structure of the metal octacyanomolybdenum compound and PBAs are greatly different from each other. Because the second transition metal molybdenum has larger radius, the compound has more abundant ion diffusion channels than PBAs, and has the potential of being used as the positive electrode of a water-based zinc ion battery. Unfortunately, the application of the materials in the aspect of the anode materials of the water-based zinc ion batteries has not been reported yet. Manganese octacyanomolybdate (Mn 2[Mo(CN)8) is a typical representative of metal octacyanomolybdenum compounds, and Carbon Nanotubes (CNTs) have advantages of excellent conductivity, high electrochemical stability, large specific surface area, and the like. The (Mn 2[Mo(CN)8) and the carbon nano tube are compounded to prepare the composite electrode material, so that the problems of structural collapse, poor conductivity and the like of the material in the charge and discharge process can be solved, and a new way is provided for designing and developing the high-performance water-based zinc ion battery anode material. Disclosure of Invention Aiming at the defects in the prior art, the invention aims to provide a preparation method of an octacyanomanganese molybdate nanoparticle/carbon nano tube (Mn 2[Mo(CN)8/CNTs) composite material. Technical proposal A preparation method of an octacyanomanganous molybdate nanoparticle/carbon nano tube (Mn 2[Mo(CN)8 ]/CNTs) composite material comprises the following steps: (1) Stirring carboxylated multiwall carbon nanotubes, and ultrasonically dispersing the carboxylated multiwall carbon nanotubes in deionized water to obtain a Carbon Nanotube (CNTs) dispersion liquid, namely a solution A, wherein the mass-volume ratio of the carbon