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US-20260128325-A1 - SOLID-STATE ELECTROLYTE MATERIAL AND PREPARATION METHOD THEREOF, CATHODE ACTIVE MATERIAL AND PREPARATION METHOD THEREOF, CATHODE PLATE, BATTERY, AND ELECTRICAL DEVICE

US20260128325A1US 20260128325 A1US20260128325 A1US 20260128325A1US-20260128325-A1

Abstract

The present disclosure provides a solid-state electrolyte material and a preparation method thereof, a cathode active material and a preparation method thereof, a cathode plate, a battery, and an electrical device, which are related to the field of battery technologies. The solid-state electrolyte material has a NASICON crystal structure. In an X-ray diffraction pattern of the solid-state electrolyte material, a 2θ value of a diffraction peak representing LiTi 2 (PO 4 ) 3 is decreased by 0.02° to 0.06° compared with a 2θ value of a corresponding diffraction peak in a standard pattern of LiTi 2 (PO 4 ) 3 . Thus, use of the solid-state electrolyte material enables a battery loaded with the solid-state electrolyte material to have excellent rate performance.

Inventors

  • Zongpu SHAO
  • Yafei Liu
  • Yanbin Chen

Assignees

  • BEIJING EASPRING MATERIAL TECHNOLOGY CO., LTD.

Dates

Publication Date
20260507
Application Date
20251230
Priority Date
20240621

Claims (20)

  1. 1 . A solid-state electrolyte material, wherein: the solid-state electrolyte material has a Na Super Ionic Conductor, NASICON, crystal structure; and in an X-ray diffraction pattern of the solid-state electrolyte material, a 2θ value of a diffraction peak representing LiTi 2 (PO 4 ) 3 is decreased by 0.02° to 0.06° compared with a 2θ value of a corresponding diffraction peak in a standard pattern of LiTi 2 (PO 4 ) 3 ; wherein the solid-state electrolyte material comprises Li x M 1 y M 2 z Ti u (PO 4 ) v1 (P 2 O 7 ) v2 , where: M 1 comprises at least one of the elements in Group 1 of the periodic table, excluding Li; M 2 comprises at least one of V, La, or Cr; and 1 ≤ x < 4 , 0 . 1 ≤ y ≤ 0 . 5 , 0.2 < z ≤ 0 .5 , 1 < u ≤ 5.5 , 2 ≤ v ⁢ 1 ≤ 6 , and 0.1 < v ⁢ 2 ≤ 3 .
  2. 2 . The solid-state electrolyte material according to claim 1 , wherein: the diffraction peak representing LiTi 2 (PO 4 ) 3 comprises a diffraction peak (012), a diffraction peak (104), a diffraction peak (113), and a diffraction peak (024).
  3. 3 . The solid-state electrolyte material according to claim 1 , wherein: compared with unit cell parameters, a-value and c-value, of LiTi 2 (PO 4 ) 3 , a-value of the solid-state electrolyte material is increased by 0.002 Å to 0.006 Å, and c-value of the solid-state electrolyte material is increased by 0.01 Å to 0.03 Å, respectively.
  4. 4 . The solid-state electrolyte material according to claim 1 , wherein: compared with a unit cell volume of LiTi 2 (PO 4 ) 3 , a unit cell volume of the solid-state electrolyte material is increased by 1 Å 3 to 3 Å 3 .
  5. 5 . The solid-state electrolyte material according to claim 2 , wherein: in the X-ray diffraction pattern of the solid-state electrolyte material, the solid-state electrolyte material has a diffraction peak (721) at a diffraction angle 2θ value ranging from 27.7° to 27.8°, wherein a peak intensity I 1 of the diffraction peak (721) and a peak intensity I 2 of the diffraction peak (113) satisfy 0.1≤I 1 /I 2 ≤0.5.
  6. 6 . The solid-state electrolyte material according to claim 1 , wherein: an ionic conductivity of the solid-state electrolyte material is greater than or equal to 5×10 −4 S/cm.
  7. 7 . The solid-state electrolyte material according to claim 1 , wherein: an ionic conductivity of the solid-state electrolyte material is greater than or equal to 1×10 −3 S/cm.
  8. 8 . The solid-state electrolyte material according to claim 1 , wherein: an average particle size of the solid-state electrolyte material ranges from 0.05 μm to 0.5 μm.
  9. 9 . The solid-state electrolyte material according to claim 1 , wherein: an average particle size of the solid-state electrolyte material ranges from 0.05 μm to 0.1 μm.
  10. 10 . The solid-state electrolyte material according to claim 1 , wherein: a pH value of the solid-state electrolyte material ranges from 6 to 10 at 25° C.
  11. 11 . The solid-state electrolyte material according to claim 1 , wherein: M 1 comprises at least one of K, Rb, or Cs.
  12. 12 . A method for preparing the solid-state electrolyte material according to claim 1 , the method comprising: mixing an M 2 source, a Ti source, a PO 4 3− source, a P 2 O 7 4− source, a precipitant, and a solvent, followed by co-precipitating and filtering, to obtain a precursor; and mixing the precursor with a Li source and an M 1 source, and sintering the mixture in an oxygen-containing atmosphere, to obtain the solid-state electrolyte material.
  13. 13 . The method according to claim 12 , wherein the method satisfies one of the following conditions: the oxygen-containing atmosphere comprises oxygen or air; a temperature of the sintering ranges from 600° C. to 800° C., and a duration of the sintering ranges from 4 hours to 10 hours; the M 1 source comprises at least one of an M 1 -containing oxide, an M 1 -containing phosphate, an M 1 -containing sulfate, an M 1 -containing chloride, an M 1 -containing nitrate, or an M 1 -containing carbonate; the M 2 source comprises at least one of an M 2 -containing oxide, an M 2 -containing phosphate, an M 2 -containing sulfate, an M 2 -containing chloride, an M 2 -containing nitrate, or an M 2 -containing carbonate; the Ti source comprises at least one of a Ti-containing phosphate, a Ti-containing acetate, a Ti-containing sulfate, a Ti-containing chloride, a Ti-containing nitrate, or a Ti-containing carbonate; the PO 4 3− source comprises at least one of H 3 PO 4 , NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 , (NH 4 ) 3 PO 4 , LiH 2 PO 4 , Li 2 HPO 4 , Li 3 PO 4 , NaH 2 PO 4 , Na 2 HPO 4 , or Na 3 PO 4 ; the Li source comprises at least one of lithium carbonate, lithium hydroxide, or lithium nitrate; the P 2 O 7 4− source comprises at least one of H 4 P 2 O 7 , (NH 4 ) 2 H 2 P 2 O 7 , Li 2 H 2 P 2 O 7 , or Li 4 P 2 O 7 ; and the precipitant comprises at least one of sodium hydroxide, sodium carbonate, or ammonia water.
  14. 14 . A cathode active material, comprising: a matrix; and a coating layer disposed on at least part of a surface of the matrix, wherein: the coating layer comprises the solid-state electrolyte material according to claim 1 .
  15. 15 . The cathode active material according to claim 14 , wherein the cathode active material satisfies one of the following conditions: a thickness of the coating layer ranges from 10 nm to 500 nm; based on a total mass of the cathode active material, a mass proportion of the solid-state electrolyte material ranges from 0.01% to 1%; in a Differential Scanning Calorimetry, DSC, measurement curve of the cathode active material, a temperature corresponding to an exothermic peak is greater than or equal to 220° C.; and the matrix comprises at least one of lithium cobalt oxide, lithium manganate, lithium nickel oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium manganate, lithium nickel manganate, lithium iron phosphate, lithium manganese phosphate, or lithium manganese iron phosphate.
  16. 16 . A method for preparing the cathode active material according to claim 14 , the method comprising: grinding the solid-state electrolyte material into nanoparticles, and mixing the nanoparticles with the matrix to obtain a mixture; and performing heat treatment on the mixture in an oxygen-containing atmosphere to obtain the cathode active material.
  17. 17 . The method according to claim 16 , wherein the method satisfies one of the following conditions: the oxygen-containing atmosphere comprises oxygen or air; and a temperature of the heat treatment ranges from 300° C. to 500° C., and a duration of the heat treatment ranges from 2 hours to 8 hours.
  18. 18 . A cathode plate, comprising: the cathode active material according to claim 14 .
  19. 19 . A battery, comprising at least one of the solid-state electrolyte material according to claim 1 .
  20. 20 . An electrical device, comprising the battery according to claim 19 .

Description

CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation of International Application No. PCT/CN2024/109049, filed on Jul. 31, 2024, which claims priority to and benefits of Chinese patent application No. 202410814749.3, filed with China National Intellectual Property Administration on Jun. 21, 2024. The disclosures of the aforementioned applications are hereby incorporated by reference in their entireties. FIELD The present disclosure relates to the field of batteries, and more particularly, to a solid-state electrolyte material and a preparation method thereof, a cathode active material and a preparation method thereof, a cathode plate, a battery, and an electrical device. BACKGROUND Range anxiety and battery safety issues have become pain points and major bottlenecks restricting the development of new energy vehicles. The key to iterative innovation of the next-generation power batteries with higher energy density and safer lies in the technological breakthroughs of solid-state batteries. As a core material of the solid-state battery, the comprehensive performance and an industrialization progress of a solid-state electrolyte are key factors to the development of the solid-state battery. Currently, the solid-state electrolyte with industrialization prospects mainly includes three major systems: a polymer, a sulfide, and an oxide. Among them, a sulfide electrolyte has a high conductivity, but their manufacturing cost is high and their structure is unstable, and there are huge challenges in large-scale production and integration into vehicles. A polymer solid-state electrolyte is soft in texture and easy to process, but it has a low ionic conductivity at a room temperature and cannot withstand voltages above 4.0V ANASICON-type oxide solid-state electrolyte features a stable structure, a low cost, and a relatively high voltage window, facilitating the iteration from a semi-solid-state battery, a quasi-solid-state battery, to an all-solid-state battery. However, an ionic conductivity of a current oxide solid-state electrolyte is still lower than that of the electrolyte, which affects rate performance and cycle performance of the battery. SUMMARY The present disclosure aims to solve at least one of the technical problems in the related art. To this end, an objective of the present disclosure is to provide a solid-state electrolyte material and a preparation method thereof, a cathode active material and a preparation method thereof, a cathode plate, a battery, and an electrical device. The solid-state electrolyte material has a high ionic conductivity, enabling a battery containing the solid-state electrolyte material to have excellent rate performance. In a first aspect of the present disclosure, a solid-state electrolyte material is provided. The solid-state electrolyte material has a Na Super Ionic Conductor, NASICON, crystal structure. In an X-ray diffraction pattern of the solid-state electrolyte material, a 2θ value of a diffraction peak representing LiTi2(PO4)3 is decreased by 0.020 to 0.06° compared with a 2θ value of a corresponding diffraction peak in a standard pattern of LiTi2(PO4)3. According to the solid-state electrolyte material of an embodiment of the present disclosure, the 2θ value of the diffraction peak representing LiTi2(PO4)3 is decreased by 0.02° to 0.06° compared with the 2θ value of the corresponding diffraction peak in the standard pattern of LiTi2(PO4)3. In this way, unit cell parameters and a unit cell volume of the solid-state electrolyte material are increased. As a result, a transport channel for lithium ions is widened, and the ionic conductivity of the solid-state electrolyte material can be improved, enabling the battery containing the solid-state electrolyte material to have the excellent rate performance. In addition, the solid-state electrolyte material according to the above-described embodiment of the present disclosure may also have the following additional technical features. In some embodiments of the present disclosure, the diffraction peak representing LiTi2(PO4)3 includes a diffraction peak (012), a diffraction peak (104), a diffraction peak (113), and a diffraction peak (024). Thus, the ionic conductivity of the solid-state electrolyte material can be further improved, enabling the battery containing the solid-state electrolyte material to have the excellent rate performance. In some embodiments of the present disclosure, compared with unit cell parameters, a-value and c-value, of LiTi2(PO4)3, a-value of the solid-state electrolyte material is increased by 0.002 Å to 0.006 Å, and c-value of the solid-state electrolyte material is increased by 0.01 Å to 0.03 Å, respectively. Thus, the ionic conductivity of the solid-state electrolyte material can be further improved, enabling the battery containing the solid-state electrolyte material to have the excellent rate performance. In some embodiments of the present disclosure, compared with a unit cell vo