Search

CN-122025615-A - Asymmetric hybrid mesoporous material and preparation method and application thereof

CN122025615ACN 122025615 ACN122025615 ACN 122025615ACN-122025615-A

Abstract

The invention discloses an asymmetric hybridization mesoporous material, a preparation method and application thereof, belonging to the technical field of mesoporous materials; the preparation method comprises the steps of based on a template agent, a pore-expanding agent and an organosilicon source, combining the SiO 2 nanospheres and an organosilane end-capping agent to prepare the super-structure silicon spheres, dispersing the super-structure silicon spheres in an alcohol-water mixed solvent, adding dopamine hydrochloride and carrying out in-situ polymerization under the action of ammonia water to obtain the asymmetric mesoporous material. The mesoporous super-structure silicon sphere constructed by the SiO 2 nanospheres is used as one end, the polydopamine layer is used as the other end, and the mesoporous super-structure silicon sphere has a high specific surface area and a rich hierarchical pore structure. The invention has simple process and mild condition, and can control the shape and the size of the material by adjusting the reaction parameters. The material is applied to the negative electrode of the water-based zinc ion battery, can obviously improve the specific capacity, the circulation stability and the multiplying power performance of the battery, effectively inhibit the growth and the side reaction of zinc dendrite, and has important energy storage application value.

Inventors

  • ZHAO ZAIWANG
  • LI HAO
  • ZHAO YUJUAN
  • LIANG DANLI
  • QI ZHENG
  • ZHAO MAN
  • YUAN QINGYUN
  • ZHAO DONGYUAN

Assignees

  • 内蒙古大学

Dates

Publication Date
20260512
Application Date
20260413

Claims (10)

  1. 1. The preparation method of the asymmetric hybridization mesoporous material is characterized by comprising the following steps of: Firstly, dissolving a template agent in an inorganic acid solution with the concentration of 1-8mol/L, uniformly stirring to form a template agent solution with the concentration of 1.5-5wt%, then adding a pore-enlarging agent into the template agent solution and continuously stirring for 2-24 hours to form nano emulsion, adding an organosilicon source, stirring and reacting for 0.5-10 hours in a normal temperature environment, then adding SiO 2 nanospheres with the particle size of 200-500nm, continuously stirring and reacting for 1-10 hours, then adding an organosilane end-capping agent, stirring and reacting for 2-24 hours to obtain a mixed solution, and finally, sequentially centrifuging, washing and drying the mixed solution to obtain the super-structure silicon spheres; step two, preparing dispersion liquid, namely dispersing the super-structure silicon spheres obtained in the step one in a mixed solvent of alcohol and water, wherein the volume ratio of the alcohol to the water is 1:1, and fully dispersing to form clear and transparent dispersion liquid; and thirdly, synthesizing an asymmetric material, namely adding ammonia water into the solution obtained in the second step, continuously stirring for 0.5-10h at room temperature, and separating, washing and drying after the reaction is finished to obtain the asymmetric mesoporous material.
  2. 2. The method for preparing the asymmetric hybrid mesoporous material according to claim 1, wherein in the first step, the mass ratio of the template agent, the pore-expanding agent, the organosilicon source, the SiO 2 nanospheres and the organosilane end-capping agent is 5-7:5-7:5-7:1-2:2-3, and the stirring speed is 50-15000r/min.
  3. 3. The method for preparing an asymmetric hybrid mesoporous material according to claim 1, wherein the template agent is one or more of F127, F68, F98 (EO 132 -PO 45 -EO 132 ), P85, P123, F108, F88, F87; The pore-expanding agent is one or more of benzene, toluene and trimethylbenzene; The organic silicon source is one or more of tetraethyl orthosilicate, 1, 2-bis (triethoxysilyl) ethane and dimethyl dimethoxy silane; The organosilane end capping agent is one or more of dimethyl dimethoxy silane and dimethyl diethoxy silane.
  4. 4. The method for preparing an asymmetric hybridization mesoporous material according to claim 1, wherein in the first step, the inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, hydroiodic acid, hydrobromic acid and hydrofluoric acid.
  5. 5. The method for preparing an asymmetric hybridization mesoporous material according to claim 1, wherein in the first step, the centrifugation speed is 5000-10000rpm, and the centrifugation time is 8-15min.
  6. 6. The method for preparing an asymmetric hybrid mesoporous material according to claim 1, wherein in the first step, distilled water is used for 1 to 5 times, and then absolute ethyl alcohol is used for 1 to 5 times.
  7. 7. The method for preparing an asymmetric hybrid mesoporous material according to claim 1, wherein in the first step, the drying treatment is to disperse the washed product in absolute ethyl alcohol to prepare an alcohol dispersion liquid with a concentration of 0.1-0.5mol/L, and then to volatilize the solvent at 40-80 ℃ for 2-48 hours.
  8. 8. The method for preparing an asymmetric hybridization mesoporous material according to claim 1, wherein in the second step, the mass ratio of dopamine hydrochloride to the super-structure silicon spheres is 0.5:1-5:1.
  9. 9. The asymmetric hybrid mesoporous material is characterized by being obtained by the preparation method of any one of claims 1-8, and has an asymmetric structure, wherein a mesoporous super-structure silicon sphere constructed by taking SiO 2 nanospheres as cores is taken as one end, a polydopamine layer generated by in-situ polymerization is taken as the other end, and the size of the polydopamine layer is 130-280nm.
  10. 10. The use of an asymmetric hybrid mesoporous material according to claim 9 in a negative electrode material of an aqueous zinc ion battery.

Description

Asymmetric hybrid mesoporous material and preparation method and application thereof Technical Field The invention belongs to the technical field of mesoporous materials, and particularly relates to an asymmetric hybrid mesoporous material, and a preparation method and application thereof. Background The water-based zinc ion battery is a research hot spot of the next generation energy storage system due to high safety, low cost and environmental friendliness. However, further development is limited by electrode materials, which have problems of low specific capacity, poor cycle stability, slow ion diffusion rate, and the like. The mesoporous material can effectively improve the ion transmission rate and the electrochemical performance due to the high specific surface area and rich pore canal structures. However, the conventional mesoporous materials are generally symmetrical in structure, and it is difficult to satisfy the requirements of high conductivity and high specific capacity at the same time. The asymmetric mesoporous material can realize a synergistic effect by combining two or more materials with different functions, and the battery performance is remarkably improved. However, the preparation method of the asymmetric mesoporous material is complex at present, and the application research in the water-based zinc ion battery is less. Therefore, a simple and efficient preparation method of the asymmetric mesoporous material is developed, and the application of the asymmetric mesoporous material in the water-based zinc ion battery is explored, so that the asymmetric mesoporous material has important scientific significance and practical value. Disclosure of Invention Aiming at the defects existing in the prior art, the invention aims to provide an asymmetric hybridization mesoporous material, a preparation method and application thereof, wherein the material has high specific surface area, rich pore channel structure and excellent electrochemical performance. The asymmetric hybrid mesoporous material is applied to the negative electrode of the water-based zinc ion battery, so that the specific capacity, the cycling stability and the multiplying power performance of the battery are improved. The invention is realized by the following technical scheme: in a first aspect, the invention provides a method for preparing an asymmetric hybrid mesoporous material, comprising the following steps: Firstly, dissolving a template agent in an inorganic acid solution with the concentration of 1-8mol/L, uniformly stirring to form a template agent solution with the concentration of 1.5-5wt%, then adding a pore-enlarging agent into the template agent solution and continuously stirring for 2-24 hours to form nano emulsion, adding an organosilicon source, stirring and reacting for 0.5-10 hours in a normal temperature environment, then adding SiO 2 nanospheres with the particle size of 200-500nm, continuously stirring and reacting for 1-10 hours, then adding an organosilane end-capping agent, stirring and reacting for 2-24 hours to obtain a mixed solution, and finally, sequentially centrifuging, washing and drying the mixed solution to obtain the super-structure silicon spheres; step two, preparing dispersion liquid, namely dispersing the super-structure silicon spheres obtained in the step one in a mixed solvent of alcohol and water, wherein the volume ratio of the alcohol to the water is 1:1, and fully dispersing to form clear and transparent dispersion liquid; and thirdly, synthesizing an asymmetric material, namely adding ammonia water into the solution obtained in the second step, continuously stirring for 0.5-10h at room temperature, and separating, washing and drying after the reaction is finished to obtain the asymmetric mesoporous material. In the first step, the mass ratio of the template agent, the pore-expanding agent, the organosilicon source, the SiO 2 nanospheres and the organosilane end-capping agent is 5-7:5-7:5-7:1-2:2-3, and the stirring speed is 50-15000r/min. Further, the template agent is one or more of F127(EO106-PO70-EO106)、F68（EO132-PO30-EO132）、F98（EO132-PO45-EO132）、P85（EO26-PO39-EO20）、P123（EO20-PO70-EO20）、F108（EO132-PO50-EO132）、F88（EO132-PO40-EO132）、F87（EO106-PO40-EO106）; The pore-expanding agent is one or more of benzene, toluene and trimethylbenzene; The organic silicon source is one or more of tetraethyl orthosilicate, 1, 2-bis (triethoxysilyl) ethane and dimethyl dimethoxy silane; The organosilane end capping agent is one or more of dimethyl dimethoxy silane and dimethyl diethoxy silane. In the first step, the inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, hydroiodic acid, hydrobromic acid and hydrofluoric acid. Further, in the first step, the speed of centrifugation is 5000-10000rpm, and the centrifugation time is 8-15min. In the first step, distilled water is used for washing for 1-5 times, and then absolute ethyl alcohol is used for washing for