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CN-119695126-B - Magnesium battery cycle stability reinforcing material and application thereof

CN119695126BCN 119695126 BCN119695126 BCN 119695126BCN-119695126-B

Abstract

The invention discloses a magnesium battery cycle stability reinforcing material, which is prepared by dissolving a proper amount of vanadium source and surfactant in a mixed solution of isopropyl alcohol and diethylene glycol, and performing solvothermal reaction and then calcining. The method has the advantages of high production efficiency, large production quantity, quick preparation time, low cost and good repeatability, and can avoid the problem of stacking and agglomerating of the traditional sheet V 2 O 5 . The coral V 2 O 5 nanometer material is used as the magnesium battery anode material, and the open three-dimensional porous structure not only increases the attachment sites of ions, but also provides a multi-channel path for the transfer of electrons. In addition, the exposed (110) crystal face reduces the interface side reaction between the electrode and the surface of the electrolyte, and reduces the generation of passivation film on the surface of the electrode, thereby accelerating the oxidation-reduction reaction of the battery, having very high capacity storage and good rate capability, and being an excellent magnesium battery anode material.

Inventors

  • LIU FANFAN
  • HU JUNHUA
  • LEI HONGHONG
  • Ban Jinjin
  • LI RONGRONG

Assignees

  • 郑州大学
  • 郑州佛光发电设备股份有限公司

Dates

Publication Date
20260505
Application Date
20241226

Claims (8)

  1. 1. The preparation method of the magnesium battery cycle stability reinforcing material is characterized by comprising the following steps of: 1) Dissolving a proper amount of vanadium source and surfactant in a mixed solution of isopropyl alcohol and diethylene glycol to obtain a solution A; 2) Carrying out hydrothermal reaction on the solution A for 18-24 hours at 180-200 ℃; 3) Washing and drying after the hydrothermal reaction to obtain a precursor powder material; 4) Heating the precursor powder material to 400-500 ℃, preserving heat for 2 hours, and cooling to obtain the precursor powder material; The vanadium source in the step 1) is NH 4 VO 3 and/or commercial V 2 O 5 powder; The surfactant in the step 1) is one or more of citric acid monohydrate, polyvinylpyrrolidone and cetyltrimethylammonium bromide; The prepared material is coral V 2 O 5 with average diameter of 5 μm; The coral V 2 O 5 is prepared into a positive electrode material of a magnesium battery, a magnesium foil is used as a battery negative electrode, a 2032 button battery is assembled, after 100 circles of charge-discharge cycles under the current density of 50 mA g -1 , the capacity is kept at 102.4 mAh g -1 , and under the current density of 500 mA g -1 , the capacity of 78.9 mAh g -1 can still be kept.
  2. 2. The preparation method of claim 1, wherein the mass ratio of the vanadium source to the surfactant in the step 1) is 1:2-4.
  3. 3. The method according to claim 1, wherein the volume ratio of isopropyl alcohol to diethylene glycol in step 1) is 1:0.5-2.
  4. 4. The preparation method according to claim 1, wherein in the step 1), the water bath with the temperature of 100+/-15 ℃ is used for heating and magnetic stirring until the water is completely dissolved, and the magnetic stirring time is 1-1.5 h.
  5. 5. The preparation method according to claim 1, wherein in step 3), ethanol is used for 3 to 5 times, and then the precipitate is frozen in a refrigerator for 8 to 12 hours and then lyophilized at-55±10 ℃ for 10 to 24 hours.
  6. 6. The method according to claim 1, wherein in step 4), the temperature is raised to the heating temperature in a muffle furnace at a temperature raising rate of 5-10 ℃ per minute.
  7. 7. A magnesium battery cycle stability enhancing material prepared by the method of any one of claims 1 to 6.
  8. 8. Use of the magnesium battery cycle stability enhancing material of claim 7 in a magnesium battery.

Description

Magnesium battery cycle stability reinforcing material and application thereof Technical Field The invention belongs to the technical field of novel energy storage, and particularly relates to a magnesium battery cycle stability reinforcing material (particularly a coral-shaped V 2O5 -based magnesium battery positive electrode material), a preparation method and application thereof in a magnesium battery. Background In recent years, along with the continuous exploration and development of clean energy and renewable energy (solar energy, wind energy, tidal energy and the like), efficient energy storage systems have received attention from researchers. V 2O5 is widely used in various types of batteries, such as lithium ion batteries, lead acid batteries, and the like, due to its excellent performance. V 2O5 is used as a positive electrode material in a battery, has high specific capacity and excellent cycle performance, and has wide application prospect in the aspects of improving the battery performance and prolonging the service life. V 2O5 is used as a transition metal oxide, has rich reserves, low cost and good safety, and compared with other electrode materials, the specific capacity of V 2O5 is up to 300mAh/g, which is several times of that of a plurality of materials. In addition, when the cyclic test is carried out at normal temperature, the capacity retention rate of V 2O5 is as high as more than 85%. V 2O5 has been widely used in recent years in a variety of new battery fields, especially zinc ion batteries, and exhibits excellent ion storage capacity, exhibiting extraordinary capacity and rate performance. Due to the diversity of V 2O5 preparations, various forms of V 2O5 have been developed, such as sea urchin, windmill, fiber spun thread, and the like. These morphologies optimize the electrochemical performance of the cell to some extent, and even further promote redox reactions through the exposed active sites. However, the low ion diffusion coefficient, low conductivity and unstable structure caused by repeated ion intercalation/deintercalation of the V 2O5 cathode material relatively limit the application thereof in metal ion batteries. Researchers have developed a series of studies to solve these problems by modification methods such as morphology control, crystal structure modification, chemical pre-insertion, and compounding with other materials. For example, chinese patent No. 118825249a discloses an amorphous carbon coated three-dimensional porous cellular VO 2/V2O5 composite material, which provides multiple active sites while an outer layer is coated with carbon, and a three-dimensional conductive network formed by cross-linking between them effectively improves the ionic conductivity and the electronic conductivity of the electrode system. CN118598186a discloses a V 2O5/HxV2O5 composite cathode material, which expands the diffusion path of Zn 2+ through proton insertion, weakens the influence of the interaction of Zn 2+ and V 2O5 lattice, and improves the rate capability of the water-based zinc ion battery. In all research methods, improving the morphology of V 2O5 is the simplest and most convenient method for improving the electrochemical performance of a battery, and the capability of absorbing metal ions is enhanced by micro-regulation and control of the morphology in the preparation process. At present, researchers have improved the morphology through methods such as electrostatic spinning, chemical vapor deposition technology, hydrothermal method and the like, but V 2O5 still has the defects of poor conductivity, unstable structure and the like, and even serious accumulation sometimes occurs, so that the structure collapses. Therefore, developing a preparation method with stable structure and economical efficiency is still an important project for future research. Based on this, the present application has been developed. Disclosure of Invention Aiming at the problems existing in the traditional preparation method, the invention provides a preparation method of a magnesium battery cycle stability enhancing material. The V 2O5 nano material prepared by the solvothermal method is used as a magnesium battery anode material, has a super-porous structure and an ion transmission channel, has a three-dimensional size of only about 5um, solves the problem of stacking and agglomerating of V 2O5 nano sheets in the traditional preparation process, effectively improves the surface active state, exposes more active sites, provides a plurality of short channel paths for rapid transfer of electrons, and has excellent cycle stability. The invention also provides the magnesium battery cycle stability reinforcing material and application thereof in a magnesium battery. Based on the above purpose, the invention adopts the following technical scheme: A preparation method of a magnesium battery cycle stability reinforcing material comprises the following steps: 1) Dissolving a proper amount of vanadi