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CN-122000437-A - Oxychloride solid electrolyte and preparation method and application thereof

CN122000437ACN 122000437 ACN122000437 ACN 122000437ACN-122000437-A

Abstract

The embodiment of the invention relates to a oxychloride solid electrolyte and a preparation method and application thereof, wherein the preparation method comprises the steps of determining stoichiometric ratio of zirconium tetrachloride, lithium oxide and anhydrous lithium chloride according to Li 2.5‑x ZrC l 5.5‑x O 0.5 , (x is more than or equal to 0 and less than or equal to 0.75), mixing uniformly, preprocessing to obtain a first mixture, a second mixture and a third mixture, respectively performing first ball milling treatment on the first mixture, the second mixture and the third mixture in a ball milling tank to obtain intermediate products Li 4 ZrC l 4 O 2 、Li ZrC l 5 and Li 2 ZrC l 6 , uniformly mixing the intermediate products Li 4 ZrC l 4 O 2 、Li ZrC l 5 and Li 2 ZrC l 6 according to a preset ratio, performing second ball milling treatment in the ball milling tank to obtain a oxychloride solid electrolyte precursor, and sintering the oxychloride solid electrolyte precursor to obtain the oxychloride solid electrolyte.

Inventors

  • DING JIN
  • SHI YONGMING
  • LIU BAINAN
  • LUO FEI

Assignees

  • 溧阳天目先导电池材料科技有限公司

Dates

Publication Date
20260508
Application Date
20241101

Claims (10)

  1. 1. A method for preparing a solid state oxychloride electrolyte, the method comprising: According to Li 2.5-x ZrCl 5.5-x O 0.5 , (x is more than or equal to 0 and less than or equal to 0.75), determining the stoichiometric ratio of zirconium tetrachloride, lithium oxide and anhydrous lithium chloride, mixing uniformly, and then preprocessing to obtain a first mixture, a second mixture and a third mixture; Respectively performing first ball milling treatment on the first mixture, the second mixture and the third mixture in a ball milling tank to obtain intermediate products Li 4 ZrCl 4 O 2 、LiZrCl 5 and Li 2 ZrCl 6 ; Uniformly mixing the intermediate products Li 4 ZrCl 4 O 2 、LiZrCl 5 and Li 2 ZrCl 6 according to a preset proportion, and performing secondary ball milling treatment in the ball milling tank to obtain a oxychloride solid electrolyte precursor; and sintering the precursor of the oxychloride solid electrolyte to obtain the oxychloride solid electrolyte.
  2. 2. The method according to claim 1, wherein the predetermined ratio is 0.25:0.75-b, wherein 0≤b≤0.75.
  3. 3. The preparation method according to claim 1, wherein the stoichiometric ratio of zirconium tetrachloride, lithium oxide and anhydrous lithium chloride is determined according to the stoichiometric ratio of Li 2.5-x ZrCl 5.5-x O 0.5 (0≤x≤0.75), and specifically comprises the following steps: determining the stoichiometric ratio of the intermediate product according to the stoichiometric ratio of Li 2.5-x ZrCl 5.5-x O 0.5 (x is more than or equal to 0 and less than or equal to 0.75); and determining the stoichiometric ratio of zirconium tetrachloride, lithium oxide and anhydrous lithium chloride according to the stoichiometric ratio of the intermediate product, and proportioning.
  4. 4. The method of claim 1, wherein the pretreatment comprises grinding and drying; The grinding is specifically that the raw materials are placed in a mortar and ground for 1 to 3 hours under inert atmosphere; The drying is specifically carried out in a vacuum drying oven at 100-150 ℃ for 2-4 hours.
  5. 5. The preparation method of the zirconium ball according to claim 1, wherein the size of the zirconium ball subjected to the first ball milling treatment is 3mm-10mm, and the ball material mass ratio is M1, wherein M is more than or equal to 4 and less than or equal to 20.
  6. 6. The method according to claim 1, wherein the first ball milling process is performed at a rotational speed of 200r/min to 2400r/min for a period of 5 hours to 70 hours.
  7. 7. The method of claim 1, wherein the sintering is performed at a temperature of 200 ℃ to 400 ℃ for a time of 2 hours to 12 hours.
  8. 8. The method according to claim 1, wherein the atmosphere of the ball milling pot is any one of a vacuum atmosphere, a nitrogen atmosphere, and an argon atmosphere.
  9. 9. A solid oxychloride electrolyte, characterized in that the solid oxychloride electrolyte is prepared by the preparation method of any one of the above claims 1 to 8.
  10. 10. A lithium ion battery comprising the oxychlorides solid state electrolyte of claim 9.

Description

Oxychloride solid electrolyte and preparation method and application thereof Technical Field The invention relates to the technical field of materials, in particular to a oxychloride solid electrolyte, a preparation method and application thereof. Background The lithium ion battery is widely applied to industrial manufacture and daily life due to high energy density and high output power. However, the traditional lithium ion liquid battery has potential safety hazards such as inflammability, explosiveness and the like, and causes great danger to life and health of people. The full solid lithium ion battery can greatly improve the safety performance of the battery and solve the problem of inflammability and explosiveness of the liquid battery. Solid state electrolytes are an important component in all-solid state lithium ion batteries. Among the many solid-state electrolytes, halide electrolytes have received attention due to their excellent physicochemical properties of high ionic conductivity, wide electrochemical window, and low interface resistance. However, some halides such as bromide, iodide, etc. are prepared under severe conditions and the ionic conductivity is not as high as chloride. Although Li 2ZrC l6 in the chloride solid-state electrolyte has an ionic conductivity of 0.2×10 -3～0.4×10-3mS·cm-1 at room temperature, further improvement in the conductivity is required to facilitate its use in all-solid-state lithium batteries. Disclosure of Invention Aiming at the defects existing in the prior art, the invention provides a oxychloride solid electrolyte, and a preparation method and application thereof. To achieve the above object, in a first aspect, the present invention provides a method for producing a oxychlorides solid electrolyte, the method comprising: According to Li 2.5-xZrC l5.5-xO0.5, (x is more than or equal to 0 and less than or equal to 0.75), determining the stoichiometric ratio of zirconium tetrachloride, lithium oxide and anhydrous lithium chloride, mixing uniformly, and then preprocessing to obtain a first mixture, a second mixture and a third mixture; Respectively performing first ball milling treatment on the first mixture, the second mixture and the third mixture in a ball milling tank to obtain intermediate products Li 4ZrC l4O2、L i ZrC l 5 and L i 2ZrC l 6; Uniformly mixing the intermediate products L i 4ZrC l4O2、Li ZrC l5 and L i 2ZrC l 6 according to a preset proportion, and performing secondary ball milling treatment in the ball milling tank to obtain a oxychloride solid electrolyte precursor; and sintering the precursor of the oxychloride solid electrolyte to obtain the oxychloride solid electrolyte. Preferably, the preset ratio is 0.25:0.75-b:b, wherein b is more than or equal to 0 and less than or equal to 0.75. Preferably, the stoichiometric ratio of zirconium tetrachloride, lithium oxide and anhydrous lithium chloride is determined according to the stoichiometric ratio of Li 2.5-xZrC l5.5-xO0.5 (x is more than or equal to 0 and less than or equal to 0.75), and the method specifically comprises the following steps: Determining the stoichiometric ratio of the intermediate product according to L i 2.5-xZrC l5.5-xO0.5 (x is more than or equal to 0 and less than or equal to 0.75) stoichiometric ratio; and determining the stoichiometric ratio of zirconium tetrachloride, lithium oxide and anhydrous lithium chloride according to the stoichiometric ratio of the intermediate product, and proportioning. Preferably, the pretreatment comprises grinding and drying; The grinding is specifically that the raw materials are placed in a mortar and ground for 1 to 3 hours under inert atmosphere; The drying is specifically carried out in a vacuum drying oven at 100-150 ℃ for 2-4 hours. Preferably, the size of the zirconium balls subjected to the first ball milling treatment is 3mm-10mm, and the ball material mass ratio is M1, wherein M is more than or equal to 4 and less than or equal to 20. Preferably, the rotation speed of the first ball milling treatment is 200r/min-2400r/min, and the time is 5 hours-70 hours. Preferably, the sintering temperature is 200-400 ℃ and the sintering time is 2-12 hours. Preferably, the atmosphere of the ball milling tank is any one of vacuum atmosphere, nitrogen atmosphere and argon atmosphere. In a second aspect, the present invention provides a solid state oxychloride electrolyte, which is prepared by the method of any one of the first aspects. In a third aspect, the present invention provides a lithium ion battery comprising the oxychloride solid state electrolyte of the second aspect described above. According to the preparation method of the oxychloride solid electrolyte, provided by the embodiment of the invention, the stoichiometric ratio of the raw materials is determined through the stoichiometric ratio of the target product, different raw materials are respectively mixed and then subjected to first ball milling to obtain an oxygen doped intermediat