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CN-121974398-A - Zeta-V of tunnel structure2O5Material, preparation method and application thereof

CN121974398ACN 121974398 ACN121974398 ACN 121974398ACN-121974398-A

Abstract

The invention belongs to the technical field of electrochemical separation materials, and particularly discloses a zeta-V 2 O 5 material with a tunnel structure, a preparation method and application thereof. The zeta-V 2 O 5 with the one-dimensional tunnel structure is successfully constructed by taking alpha-V 2 O 5 and silver salt as precursors through a two-step hydrothermal method. The preparation method is simple, raw materials are easy to obtain, reaction conditions are mild, the crystal structure of the product is stable, the purity is high, and the problem that pure phase zeta-V 2 O 5 is difficult to obtain by the traditional method is solved. The prepared zeta-V 2 O 5 has specific gap sites, has excellent selective insertion capability on lithium ions, solves the problems of high energy consumption, large pollution and the like in the traditional lithium isotope separation process by adopting the method for efficiently separating the Li isotopes through the mixed capacitance deionization technology, and provides a new way for obtaining the green low carbon of the nuclear fusion fuel 6 Li.

Inventors

  • LIU QINGZHU
  • LI CONGCONG
  • ZHANG XINYUAN
  • Tai Wanyu
  • LI MING

Assignees

  • 中国科学院合肥物质科学研究院

Dates

Publication Date
20260505
Application Date
20260408

Claims (10)

  1. 1. The preparation method of the zeta-V 2 O 5 material with the tunnel structure is characterized by comprising the following steps of: Step S1, uniformly mixing alpha-V 2 O 5 vanadium oxide powder and a silver salt precursor through mechanical ball milling to obtain a mixed material; S2, carrying out hydrothermal reaction on the obtained mixture, and reacting for 48-96 hours at 150-250 ℃ to generate a beta-Ag x V 2 O 5 intermediate, wherein x is more than or equal to 0.2 and less than or equal to 0.5; And S3, treating the beta-Ag x V 2 O 5 intermediate by adopting inorganic acid, and reacting for 12-36 hours at 160-200 ℃ to enable silver ions to be de-intercalated, so as to prepare the zeta-V 2 O 5 material with the tunnel structure.
  2. 2. The method for preparing a zeta-V 2 O 5 material with a tunnel structure according to claim 1, wherein in step S1, the silver salt precursor is one or more of silver acetate, silver nitrate or silver oxide, and the molar ratio of alpha-V 2 O 5 to silver salt is 1 (0.2-0.5).
  3. 3. The process for preparing a zeta-V 2 O 5 material having a tunnel structure according to claim 1 or 2, wherein in step S2, the hydrothermal reaction is carried out in a closed autoclave at a reaction temperature of 200-220 ℃ for a reaction time of 60-84 hours.
  4. 4. The method for preparing a zeta-V 2 O 5 material according to claim 1, wherein in step S3, the mineral acid is one of hydrochloric acid, nitric acid and sulfuric acid, and the concentration thereof is 0.1-2.0 mol/L.
  5. 5. The method for preparing a zeta-V 2 O 5 material according to claim 4, wherein in step S3, the inorganic acid is hydrochloric acid with a concentration of 0.5-1.5 mol/L, and the reaction temperature is 180-190 ℃.
  6. 6. The method for preparing a zeta-V 2 O 5 material according to claim 1, wherein in step S3, after silver ion deintercalation, the product is washed with a sodium thiosulfate solution to remove residual silver compounds, and then sequentially washed alternately with deionized water and an organic solvent, and finally dried at 50-100 ℃ for 4-24 hours.
  7. 7. The method for preparing a zeta-V 2 O 5 material with a tunnel structure according to claim 1, wherein the mechanical ball milling is performed by zirconia or agate balls, the ball-to-material ratio is (5-20): 1, and the ball milling time is 20-60 minutes.
  8. 8. The method for preparing a zeta-V 2 O 5 material according to claim 1, wherein the hydrothermal reaction solvent is deionized water, and the solid-to-liquid ratio is 1 (10-50) g/mL.
  9. 9. A ζ -V 2 O 5 material of a tunnel structure manufactured by the method for manufacturing ζ -V 2 O 5 material of a tunnel structure according to any one of claims 1 to 8, wherein ζ -V 2 O 5 material of the tunnel structure has a monoclinic structure, and a space group is C2/m.
  10. 10. Use of the zeta-V 2 O 5 material of a tunnel structure according to claim 9 in an electrochemical lithium isotope separation electrode.

Description

Zeta-V 2O5 material with tunnel structure and preparation method and application thereof Technical Field The invention belongs to the technical field of electrochemical separation materials, and particularly discloses a zeta-V 2O5 material with a tunnel structure, a preparation method thereof and application of the zeta-V 2O5 material in an electrochemical lithium isotope separation electrode. Background The separation of lithium isotopes 6 Li and 7 Li is a key challenge in the nuclear energy industry. 6 Li is used as a core raw material for tritium proliferation reaction, the demand of fusion reactor can be met when the abundance is higher than 30%, and 7 Li is used as a pH regulator in a pressurized water reactor, so that the purity is higher than 99.9%. At present, the mainstream separation technology such as amalgam method (COLEX technology) relies on mercury as a medium, and has the problems of heavy metal pollution, high energy consumption, complex operation and the like. Although the solvent extraction method avoids mercury, crown ether extractant has high cost, easy damage, low single-stage separation factor and multiple stages of serial connection to realize effective enrichment. Ion exchange chromatography is simple and convenient to operate, but has slow equilibrium dynamics and poor stationary phase stability, so that the industrial application of the ion exchange chromatography is limited. In recent years, adsorption methods have been attracting attention for green and efficient use, wherein layered materials (such as LiAl-LDHs) and Metal Organic Frameworks (MOFs) are used for lithium adsorption, but have drawbacks of low adsorption capacity, insufficient cycle stability, and the like. The tunnel structure vanadium oxide serves as an emerging insertion host, and a unique 1D tunnel can accommodate lithium ions and realize selective adsorption through a Faraday process. Studies show that zeta-V 2O5 has high theoretical capacity, multiple electron redox activity and excellent water stability. However, the prior art does not systematically solve the problems of interface design, diffusion dynamics regulation and scale application of zeta-V 2O5 in lithium isotope separation. Particularly, a high-selectivity enrichment method aiming at 6Li/7 Li isotope effect is lacked, the device integration level is low, and the practical flow channel operation requirement is difficult to meet. Disclosure of Invention In view of the shortcomings in the prior art, one of the purposes of the invention is to provide a preparation method of a zeta-V 2O5 material with a tunnel structure, which is to treat a vanadium oxide precursor through controllable hydrothermal reaction and a topochemical deintercalation process, so as to realize the preparation of the zeta-V 2O5 material with high purity and high crystallinity. The preparation process is simple, the reaction process is easy to control, the product stability is good, and the problems of complex synthesis path, low phase purity and the like of the current zeta-phase vanadium pentoxide are solved. In order to achieve the purpose, the invention adopts the following technical scheme that the preparation method of the zeta-V 2O5 material with the tunnel structure comprises the following steps: Step S1, uniformly mixing alpha-V 2O5 vanadium oxide powder and a silver salt precursor through mechanical ball milling to obtain a mixed material; S2, carrying out hydrothermal reaction on the obtained mixture, and reacting for 48-96 hours at 150-250 ℃ to generate a beta-Ag xV2O5 intermediate, wherein x is more than or equal to 0.2 and less than or equal to 0.5; And S3, treating the beta-Ag xV2O5 intermediate by adopting inorganic acid, and reacting for 12-36 hours at 160-200 ℃ to enable silver ions to be de-intercalated, so as to prepare the zeta-V 2O5 material with the tunnel structure. The preparation method of the zeta-V 2O5 material used as the tunnel structure is further improved: Preferably, in step S1, the silver salt precursor is one or more of silver acetate, silver nitrate or silver oxide, and the molar ratio of α -V 2O5 to silver salt is 1 (0.2-0.5). Preferably, in step S2, the hydrothermal reaction is performed in a closed high-pressure reaction kettle, the reaction temperature is 200-220 ℃, and the reaction time is 60-84 hours. Preferably, in step S3, the inorganic acid is one of hydrochloric acid, nitric acid or sulfuric acid, and the concentration of the inorganic acid is 0.1-2.0 mol/L. Preferably, in the step S3, the inorganic acid is hydrochloric acid with the concentration of 0.5-1.5 mol/L, and the reaction temperature is 180-190 ℃. Preferably, in step S3, after the silver ions are deintercalated, the product is washed with a sodium thiosulfate solution to remove residual silver chloride, and then is alternately washed with deionized water and an organic solvent in sequence, and finally is dried at 50-100 ℃ for 4-24 hours. Preferably, the mechanical ball milling