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CN-122010166-A - Two-dimensional ultrathin ZnIn with adjustable indium vacancies2S4Preparation method and application of nanosheet material

CN122010166ACN 122010166 ACN122010166 ACN 122010166ACN-122010166-A

Abstract

The invention discloses a preparation method and application of a two-dimensional ultrathin ZnIn 2 S 4 nano sheet material with adjustable indium vacancies, and belongs to the technical field of sodium ion battery materials. The preparation method comprises the following steps of (1) adding a zinc source, an indium source and a sulfur source into deionized water, uniformly stirring to form a reaction mixture, (2) transferring the mixed solution into a polytetrafluoroethylene reaction kettle liner, controlling the concentration of indium vacancies by regulating and controlling the hydrothermal reaction temperature, and (3) centrifuging, washing and drying the obtained mixed substance to obtain the two-dimensional ultrathin ZnIn 2 S 4 nano sheet material with adjustable indium vacancies. The negative electrode material of the sodium ion battery has excellent quick charge capability, high specific capacity, excellent multiplying power performance and excellent cycle stability.

Inventors

  • WU SONGPING
  • Bao Yaguang
  • LI XUE
  • LIN RUNQIANG
  • HE XIAXIAN
  • YAO XIAOYAN
  • SU ZHIHAO
  • WU SHIXI
  • SUN WENQING
  • LI YUAN

Assignees

  • 广东电驰千里新能源有限公司

Dates

Publication Date
20260512
Application Date
20260205

Claims (10)

  1. 1. The preparation method of the two-dimensional ultrathin ZnIn 2 S 4 nano sheet material with adjustable indium vacancies is characterized by comprising the following steps of: 1) Stirring and dispersing a zinc source, an indium source and a sulfur source in deionized water to form a reaction mixed solution; 2) Transferring the reaction mixed solution into a polytetrafluoroethylene reaction kettle liner for hydrothermal reaction to obtain a mixture, and centrifuging, washing and drying to obtain the two-dimensional ultrathin ZnIn 2 S 4 nano sheet material with adjustable indium vacancies.
  2. 2. The method of claim 1, wherein in step 1), the zinc source comprises one or more of zinc chloride, zinc acetate, zinc nitrate hexahydrate, and zinc acetate dihydrate.
  3. 3. The method of claim 1, wherein in step 1), the indium source is one or more of indium chloride, indium chloride tetrahydrate, indium chloride hydrate, and indium nitrate hydrate.
  4. 4. The method according to claim 1, wherein in the step 1), the sulfur source is one or more of thiourea, sulfur powder, thioacetamide and L-cysteine.
  5. 5. The method according to claim 1, wherein in the step 1), the molar ratio of the zinc source, the indium source and the sulfur source is 1:2:8.
  6. 6. The preparation method of the water-based paint, according to claim 1, wherein in the step 2), the stirring and dispersing time is 30-180 min, the hydrothermal reaction temperature is 120-180 ℃, the reaction time is 12-24 h, the washing agent used for washing is ethanol and deionized water, the drying temperature is 50-80 ℃, and the drying time is 8-24 h.
  7. 7. The two-dimensional ultrathin ZnIn 2 S 4 nanosheet material with adjustable indium vacancies prepared by the method of any of claims 1-6, wherein the indium vacancies are adjustable and the concentration of the indium vacancies can be effectively controlled by controlling the temperature of the hydrothermal reaction.
  8. 8. Use of the two-dimensional ultrathin ZnIn 2 S 4 nanosheet material with adjustable indium vacancies according to claim 7 as a negative electrode material for sodium ion batteries.
  9. 9. The application of the two-dimensional ultrathin ZnIn 2 S 4 nano sheet material with adjustable indium vacancies as a negative electrode material of a sodium ion battery, which is characterized by comprising the following steps of mixing the two-dimensional ultrathin ZnIn 2 S 4 nano sheet material with adjustable indium vacancies, acetylene black and polyvinylidene fluoride, pulping, and coating on a copper foil to obtain the negative electrode sheet of the sodium ion battery.
  10. 10. The application of the two-dimensional ultrathin ZnIn 2 S 4 nano sheet material with adjustable indium vacancies according to claim 9, which is characterized in that the application is carried out under the following conditions that the current density is 0.5-10A g 1 。

Description

Preparation method and application of two-dimensional ultrathin ZnIn 2S4 nano sheet material with adjustable indium vacancies Technical Field The invention relates to the technical field of sodium ion battery anode materials, in particular to a preparation method and application of a two-dimensional ultrathin ZnIn 2S4 nano sheet material with adjustable indium vacancies. Background Lithium Ion Batteries (LIBs) are widely used in portable devices and electric vehicles, but their use in power grid energy storage systems is limited by lithium resource shortages, maldistribution and high costs. Sodium Ion Batteries (SIBs) are of great interest due to their abundant sodium resources and similar electrochemical properties as lithium ion batteries, and are particularly suitable for large-scale energy storage. However, sodium ion batteries have low energy densities and poor cycling stability, limiting their wide application. Therefore, the development of high-performance electrode materials is critical to improving the energy density and electrochemical performance of sodium-ion batteries. Transition Metal Sulfides (TMSs) are a very potential class of materials in electrochemical energy storage materials due to their extremely high theoretical capacity and unique multi-step electron transfer mechanisms. ZnIn 2S4 (ZIS) has wide application in the energy conversion and storage fields due to its lamellar structure and tunable band aligned two-dimensional (2D) bimetal semiconductor structure. However, its practical application still faces multiple bottlenecks, including low conductivity, slow sodium ion kinetics, and significant volume expansion during electrochemical cycling, resulting in poor cycling performance and rate capability. To solve these problems, conventional modification methods focus on controlling the morphology and microstructure of the external interface to enhance the structural stability of the electrode material surface and promote diffusion kinetics of the electrode material surface, but they do not effectively promote ion/electron transport rates within the crystal structure, which limits the storage properties of these materials for sodium ions. Therefore, there is an urgent need to explore new internal tuning methods to enhance the ion/electron transport properties within the lattice structure. Vacancy engineering is an effective strategy for adjusting the electronic structure of electrode materials and improving the electrochemical performance of the electrode materials. The introduction of the vacancies can obviously improve the conductivity of electrons, reduce the activation energy of ion migration, provide more active sites, increase the adsorption and storage sites of sodium ions, and improve the specific capacity, the cycling stability and the rate performance （Se-Rich Functionalized FeSxHollow Nanospheres for Accelerated and Long-Lasting Sodium Storage, Advanced Functional Materials. 2024, 35, 2414246）. of the material, so that the regulation and control of the vacancy structure of the atomic layer is important for the development of the transition metal sulfide-based sodium ion anode material. Disclosure of Invention Aiming at the problems, the invention prepares a two-dimensional ultrathin ZnIn 2S4 nano sheet material (ultra-V In -ZIS-x) with adjustable indium vacancies and applies the two-dimensional ultrathin ZnIn 2S4 nano sheet material to a sodium ion spot cell cathode material. The ultra-V In -ZIS-x nanosheets have an ultrathin nanosheet structure. The material has the characteristics that (1) the two-dimensional ultrathin nano sheet structure increases the contact area of electrolyte, shortens the transmission path of sodium ions and electrons, and (2) the indium vacancy improves the electric conductivity of the electrons of the material, increases the adsorption and storage sites of the sodium ions, and improves the sodium storage capacity of the material. Therefore, ultra-V In -ZIS-x shows excellent electrochemical performance as a negative electrode material of a sodium ion battery. In order to achieve the technical purpose, the invention adopts the following technical scheme: The invention provides a preparation method of a two-dimensional ultrathin ZnIn 2S4 nano sheet material with adjustable indium vacancies, which is characterized by comprising the following steps: 1) Stirring and dispersing a zinc source, an indium source and a sulfur source in deionized water to form a reaction mixed solution; 2) Transferring the reaction mixed solution into a polytetrafluoroethylene reaction kettle liner for hydrothermal reaction, centrifuging, washing and drying the obtained mixture to obtain the two-dimensional ultrathin ZnIn 2S4 nano sheet material with adjustable indium vacancies. Preferably, in step 1), the zinc source comprises one or more of zinc chloride, zinc acetate, zinc nitrate hexahydrate and zinc acetate dihydrate. Preferably, in step 1), the indium source is one or more