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CN-122025753-A - Nitrogen-oxygen co-doped zirconium-based halide solid electrolyte and preparation method thereof

CN122025753ACN 122025753 ACN122025753 ACN 122025753ACN-122025753-A

Abstract

The invention discloses a nitrogen-oxygen co-doped zirconium-based halide solid electrolyte material and a preparation method thereof, wherein the chemical formula of the nitrogen-oxygen co-doped zirconium-based halide solid electrolyte material is Li 1+3x+ 2y ZrN x O y Cl 5 , x is more than or equal to 0.15 and less than or equal to 0.3, y is more than or equal to 0 and less than or equal to 0.15, 1+3x+2y+1=ax+by+5, a and b are respectively weighted average valence values of N and O, and the preparation method of the solid electrolyte material.

Inventors

  • XIAO WEI
  • Hou Zhengxi
  • LI XIFEI
  • YANG JIAXU
  • WANG JINGJING
  • WANG SULAN

Assignees

  • 西安理工大学

Dates

Publication Date
20260512
Application Date
20251130

Claims (10)

  1. 1. A nitrogen-oxygen co-doped zirconium-based halide solid state electrolyte, wherein the nitrogen-oxygen co-doped zirconium-based halide solid state electrolyte has the chemical formula Li 1+3x+2y ZrN x O y Cl 5 , wherein 0.15 +.x +.0.3 +.0.15 +≤y +.1+2y+ax+by+5, a, b are weighted average valences of N, O, respectively.
  2. 2. A nitrogen-oxygen co-doped zirconium based halide solid state electrolyte as recited in claim 1 wherein 1.75 +.1+3x+y +.1.85.
  3. 3. A nitrogen-oxygen co-doped zirconium based halide solid state electrolyte according to any one of claims 1 or 2, wherein y = 0.
  4. 4. A nitrogen-oxygen co-doped zirconium based halide solid state electrolyte according to any one of claims 1 or 2, wherein the nitrogen-oxygen co-doped zirconium based halide solid state electrolyte has the chemical formula Li 1.75 ZrN 0.15 O 0.15 Cl 5 、Li 1.8 ZrN 0.3 O 0.1 Cl 5 、Li 1.85 ZrN 0.25 O 0.05 Cl 5 or Li 1.9 ZrN 0.3 Cl 5 .
  5. 5. A method for preparing the nitrogen-oxygen co-doped zirconium-based halide solid electrolyte according to any one of claims 1 to 4, comprising the steps of: (1) Weighing LiCl and ZrCl 4 、Li 2 O、Li 3 N according to a stoichiometric ratio according to a chemical formula as raw materials; (2) And (3) carrying out mechanochemical synthesis on the raw material in the step (1) so as to obtain the nitrogen-oxygen co-doped zirconium-based halide solid electrolyte.
  6. 6. The method for preparing a nitrogen-oxygen co-doped zirconium-based halide solid electrolyte according to claim 5, wherein in the step (2), the mechanochemical synthesis method in the step (2) comprises a gradient rotational speed pre-grinding reaction and a high-energy ball milling synthesis reaction, wherein the rotational speed of the gradient rotational speed pre-grinding reaction is 100-400 rpm, the grinding time is 2-12 h, the high-energy ball milling synthesis reaction time is 16-32 h, and the ratio of the cooling time to the ball milling time of the high-energy ball milling synthesis reaction is (0.5-1): 1.
  7. 7. The method for preparing a solid electrolyte of nitrogen-oxygen co-doped zirconium-based halide according to claim 5, wherein in the step (2), the ball-to-material ratio of the high-energy ball-milling synthesis reaction in the step (2) is 25-45:1.
  8. 8. The method for preparing a nitrogen-oxygen co-doped zirconium-based halide solid electrolyte according to claim 5, wherein the ball-milling beads of the high-energy ball-milling synthesis reaction in the step (2) have a diameter of 2-10 mm, preferably the ball-milling beads have diameters of 5mm, 3mm and 2mm respectively, and the mass ratio of the three ball-milling beads is 1:1:1, preferably the ball-milling beads are zirconium oxide; and/or, the mechanochemical synthesis of step (2) is performed under an inert gas atmosphere.
  9. 9. Use of a nitrogen-oxygen co-doped zirconium-based halide solid state electrolyte according to any one of claims 1 to 4 in a solid state battery.
  10. 10. An energy storage device characterized by employing the nitrogen-oxygen co-doped zirconium-based halide solid state electrolyte according to any one of claims 1-4, wherein the energy device is any one of a battery, a battery pack, and a battery system.

Description

Nitrogen-oxygen co-doped zirconium-based halide solid electrolyte and preparation method thereof Technical Field The invention belongs to the technical field of solid electrolyte materials of lithium ion batteries, and particularly relates to a related preparation method of a nitrogen-oxygen co-doped zirconium-based halide solid electrolyte material. Background With the use and development of new electric vehicles and large-scale energy storage devices, the demand of secondary batteries with high safety, high specific energy and long service life is becoming urgent. Traditional lithium ion batteries have revolutionized the consumer electronics industry and are widely used in everyday life. However, in the present day, the industries of electric automobiles, unmanned aerial vehicles, energy storage power stations and the like develop at a high speed, the traditional liquid battery can not meet the requirements, and the solid battery is focused on the advantages of high safety, high energy density, wide working temperature range and the like. From the safety point of view, the organic electrolyte of the liquid battery is highly flammable, and once the short circuit, overcharge, overheat or mechanical damage occurs inside the battery, the electrolyte is liable to fire and serious thermal runaway and explosion of the liquid battery occur. While the electrolyte in a solid-state battery is usually a nonflammable or flame-retardant material (such as oxide, sulfide, halide), the physical and chemical properties are more stable, and the solid-state battery is safer under abusive conditions. From the energy density analysis, for safety and stability, a graphite negative electrode is generally used in a liquid battery, the theoretical specific capacity of the graphite negative electrode is lower (372 mAh g -1), the electrolyte in a solid battery is denser and has higher mechanical strength, and lithium metal (3860 mAh g -1) with high specific capacity can be used as the negative electrode, and the growth of lithium dendrites is inhibited to a certain extent, so that the energy density of the solid battery is remarkably improved. From the angle analysis of the working temperature range, the electrolyte of the liquid battery has the advantages of increased viscosity at low temperature, rapid decrease of ionic conductivity, easy decomposition and deterioration even boiling gasification at high temperature, and the solid electrolyte has good high-temperature stability, is not easy to decompose and volatilize, and certain solid electrolytes can keep good ionic conductivity at low temperature. Although the advantages of solid-state batteries are remarkable, the large-scale commercialization of solid-state batteries still faces some key technical challenges, mainly involving lower ionic conductivity of the solid-state electrolyte, limited solid-solid contact between the solid-state electrolyte and the solid electrode, and poor interfacial stability between the solid-state electrolyte and the high-voltage positive electrode and the low-voltage negative electrode, so that development of novel solid-state electrolytes with high ionic conductivity and good interfacial stability is urgently needed to synergistically improve electrochemical reversibility and reaction kinetics of the solid-state batteries. Solid-state electrolytes, which are the core in solid-state batteries, determine the intrinsic electrochemical performance of solid-state batteries, with inorganic solid-state electrolytes (oxides, sulfides, halides, etc.) having been of interest due to their higher ionic conductivity and wider electrochemical window. The oxide has higher thermodynamic/chemical stability, higher electrochemical window upper limit and ideal mechanical property, but has lower ionic conductivity, poorer interface contact capability with a solid anode material, and serious interface side reaction between partial oxide solid electrolyte and a lithium metal anode, so that the interface impedance is rapidly increased in the circulation process. Sulfide has outstanding ionic conductivity, better mechanical strength and excellent plasticity, is a novel solid electrolyte with great competitiveness, but the lower upper limit of an electrochemical window and the poor oxidation resistance lead to the difficulty of stably adapting to a high-voltage positive electrode material, and the large-scale production of the sulfide is further limited by high humidity sensitivity and severe preparation conditions. In recent years, halide solid-state electrolytes have received widespread attention in the field of solid-state batteries due to their high ionic conductivity, wide electrochemical window, and good positive electrode interfacial compatibility. At the same time, the excellent mechanical flexibility and structural plasticity of the halide can ensure good interface contact and rapid ion transmission between the halide and the solid electrode. However, the ionic co