Method for preparing sodium super ionic conductor solid electrolyte by low-dimensional crystallization

Patent metadata

Field	Value
Publication number	US-12051776-B2
Application number	US-202318537953-A
Country	US
Kind code	B2
Filing date	Dec 13, 2023
Priority date	Dec 30, 2022
Publication date	Jul 30, 2024
Grant date	Jul 30, 2024

Abstract

A method for preparing a sodium super ionic conductor solid electrolyte by low-dimensional crystallization belongs to a field of energy materials. The method is based on the theory of negative ion coordination polyhedron growth unit, and uses low-temperature plasma as a protective gas of a spray drying equipment. While evaporating the solvent in a sodium super ionic conductor solid electrolyte precursor slurry, plasma active groups modify the particle surface of the sodium super ionic conductor solid electrolyte precursor particles in-situ. A free space dimension of crystal growth in the crystallization process is reduced, and directional growth of crystals in the solid phase sintering process is induced. Secondly, the dispersion stability of the sodium super ionic conductor solid electrolyte precursor particles is improved. Compared with the traditional high-temperature solid-state sintering process, the method has the advantages of fast crystallization speed, high crystal purity and integrity, good compactness, and uniform particles.

First claim

What is claimed is:

1. Method for preparing a sodium super ionic conductor solid electrolyte by low-dimensional crystallization, comprising the following steps:
Precursor slurry preparation:
weighing raw materials according to a preset chemical formula Na x Zr 2 Si x-1 P 4-x O 12 (wherein, 1≤x≤4);
adding the raw materials into a grinding solvent to obtain a first solution;
pretreating the first solution by ball milling to obtain a second solution; and
nano treating the second solution by sand milling to obtain a sodium super ionic conductor solid electrolyte precursor slurry;

Plasma-assisted spray drying granulation:
spray-drying and granulating the sodium super ionic conductor solid electrolyte precursor slurry in a spray drying tower; and
feeding plasma atmosphere into the spray drying tower simultaneously to obtain sodium super ionic conductor solid electrolyte precursor particles with surfaces modified in-situ by plasma active groups; and

Sodium super ionic conductor solid electrolyte precursor particle sintering:
putting the sodium super ionic conductor solid electrolyte precursor particles into a muffle furnace and sintering to obtain the sodium super ionic conductor solid electrolyte.

2. The method according to claim 1 , wherein,
a sodium source in the raw material is one or more of sodium chloride, sodium carbonate, sodium thiosulfate, sodium bicarbonate, sodium nitrate, and trisodium phosphate dodecahydrate;
a zirconium source is zirconium dioxide;
a silicon source is silicon dioxide; and
a phosphorus source is one or more of ammonium dihydrogen phosphate, sodium hydrogen phosphate, and trisodium phosphate dodecahydrate.

3. The method according to claim 1 , wherein, the grinding solvent is one or more of ethanol, water, acetone, and isopropanol.

4. The method according to claim 1 , wherein, in the step of precursor slurry preparation, a rotational speed of the ball milling is 50 r/min-1000 r/min, and ball milling time is 0.5 h-48 h.

5. The method according to claim 1 , wherein, a speed of the sand-milling is 50 r/min-1500 r/min, and sand-milling time is 0.5 h-48 h.

6. The method according to claim 1 , wherein, the plasma atmosphere is one or more of nitrogen, argon, helium, nitrogen-argon mixed gas, nitrogen-helium mixed gas, and argon-helium mixed gas.

7. The method according to claim 1 , wherein, in the step of plasma-assisted spray drying and granulation, a spray drying temperature is 50° C.-300° C., and a pressure is 0 Mpa-1 Mpa.

8. The method according to claim 1 , wherein, in the step of sodium super ionic conductor solid electrolyte precursor particle sintering, a sintering temperature is 700° C.-1400° C., and sintering time is 2 h-36 h.

9. The method according to claim 1 , wherein, the sodium super ionic conductor solid electrolyte is in a form of regular hexahedral crystals with a particle size of 3 μm-4 μm.

10. A sodium super ionic conductor solid electrolyte, wherein the sodium super ionic conductor solid electrolyte is prepared by the preparation methods in claim 1 .

Assignees

• Univ Kunming Science & Technology
• Jiangsu Fengchi Carbon Based New Material Res Institute Co Ltd

Inventors

• Liang Feng
• Hou Minjie
• Zhang Da
• Zhang Tao
• Xiang Sunzu
• Jiang Wenlong
• Xu Baoqiang
• Yang Bin

Classifications

• H01M2300/0068

  inorganic · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title