Solid-state electrolyte, lithium battery comprising solid-state electrolyte, and preparation method of solid-state electrolyte

Patent metadata

Field	Value
Publication number	US-2024113327-A1
Application number	US-202318472386-A
Country	US
Kind code	A1
Filing date	Sep 22, 2023
Priority date	Sep 23, 2022
Publication date	Apr 4, 2024
Grant date	—

Abstract

A solid-state electrolyte including:
a compound represented by Formula 1

Li 5-4y Al 1-y X y O 4-4y-δ   Formula 1
wherein in Formula 1, 0.1≥y≥0.8 and 0≤δ<1, and X is Cl, Br, or a combination thereof, and wherein the compound is amorphous.

First claim

What is claimed is:

1 . A solid-state electrolyte comprising:
a compound represented by Formula 1
Li 5-4y Al 1-y X y O 4-4y-δ   Formula 1

wherein in Formula 1, 0.1≤y≤0.8 and 0≤δ<1, and X is Cl, Br, or a combination thereof, and wherein the compound is amorphous.

2 . The solid-state electrolyte of claim 1 ,
wherein the solid-state electrolyte has a first peak at a diffraction angle of 47.0±1.0° 2θ and a second peak at a diffraction angle of 35.0±1.0° 2θ, when analyzed by an X-ray diffraction using CuKα radiation, and wherein a ratio of an intensity of the second peak to an intensity of the first peak is about 3 or less.

3 . The solid-state electrolyte of claim 1 ,
wherein the solid-state electrolyte has a second peak at a diffraction angle of 35.0±1.0° 2θ and a third peak at a diffraction angle of 57.8±1.0° 2θ, when analyzed by an X-ray diffraction using CuKα radiation, and wherein a ratio of an intensity of the second peak to an intensity of the third peak is about 4 or less.

4 . The solid-state electrolyte of claim 1 ,
wherein a first full width at half maximum of a first peak of the solid-state electrolyte at a diffraction angle of 47.0±1.0° 2θ in an X-ray diffraction spectrum of the solid-state electrolyte is greater than a second full width at half maximum of a first peak of a crystalline Li 5 AlO 4 at a diffraction angle of 47.0±1.0° 2θ in an X-ray diffraction spectrum of the crystalline Li 5 AlO 4 , when measured under a same condition as the solid-state electrolyte and using CuKα radiation, and a ratio of the first full width at half maximum to the second full width at half maximum is about 1.3 or greater.

5 . The solid-state electrolyte of claim 1 ,
wherein a third full width at half maximum of a second peak of the solid-state electrolyte at a diffraction angle of 35.0±1.0° 2θ in an X-ray diffraction spectrum of the solid-state electrolyte is greater than a fourth full width at half maximum of a second peak of a crystalline Li 5 AlO 4 at a diffraction angle of 35.0±1.0° 2θ in an X-ray diffraction spectrum of the crystalline Li 5 AlO 4 , when measured under a same condition as the solid-state electrolyte and using CuKα radiation, and a ratio of the third full width at half maximum to the fourth full width at half maximum is about 1.3 or greater.

6 . The solid-state electrolyte of claim 1 , wherein a first distance between a lithium atom and an oxygen atom in the compound represented by Formula 1 is greater than a second distance between a lithium atom and an oxygen atom in an amorphous Li 5 AlO 4 ,
wherein the first distance is a distance between lithium and oxygen atoms, corresponding to a peak having a second highest proportion of the lithium and oxygen atoms in a distance distribution curve of the lithium and oxygen atoms in the compound represented by Formula 1, and wherein the second distance is a distance between lithium and oxygen atoms, corresponding to a peak having a second highest proportion of the lithium and oxygen atoms in a distance distribution curve of the lithium and oxygen atoms in the amorphous Li 5 AlO 4 .

7 . The solid-state electrolyte of claim 6 , wherein the first distance is greater than about 2.1 angstroms and the second distance is less than about 2.1 angstroms.

8 . The solid-state electrolyte of claim 1 , wherein in the compound represented by Formula 1, a proportion of lithium atoms having a third distance between the lithium atoms in the compound represented by Formula 1 is greater than a proportion of lithium atoms having a fourth distance between the lithium atoms in an amorphous Li 5 AlO 4 ,
wherein the proportion of the lithium atoms having the third distance is a proportion of the lithium atoms having a distance of about 2.5 angstroms to about 3.5 angstroms in a distance distribution curve of the lithium atoms in the compound represented by Formula 1, and the proportion of the lithium atoms having the fourth distance is a proportion of the lithium atoms having a distance of about 2.5 angstroms to about 3.5 angstroms in a distance distribution curve of the lithium atoms in the amorphous Li 5 AlO 4 .

9 . The solid-state electrolyte of claim 1 , wherein the compound represented by Formula 1 comprises an AlO 4 5− unit and an X − unit, and
the X − unit is disposed adjacent to the Li in the compound represented by Formula 1.

10 . The solid-state electrolyte of claim 9 , wherein
a proportion of the AlO 4 5 -unit is about 20 percent to about 90 percent, relative to a total content of the AlO 4 5− unit and the X − unit in the compound represented by Formula 1, and a proportion of the X − unit is about 10 percent to about 80 percent, relative to the total content of the AlO 4 5− unit and the X − unit in the compound represented by Formula 1.

11 . The solid-state electrolyte of claim 9 , wherein the compound represented by Formula 1 has an ionic conductivity at 25° C. of 1×10 −7 Siemens per centimeter or greater, and the Li in the compound represented by Formula 1 is randomly disposed within the compound.

12 . The solid-state electrolyte of claim 1 , wherein the solid-state electrolyte has an ionic conductivity at 25° C. of 1×10 −7 Siemens per centimeter or greater, and the solid-state electrolyte has a lithium diffusion barrier of 625 millielectronvolts or less.

13 . The solid-state electrolyte of claim 1 , wherein the solid-state electrolyte is free of LiI or iodine, and
is electrochemically stable at a voltage of 3.0 volts or greater as compared to lithium metal.

14 . The solid-state electrolyte of claim 1 , wherein in the compound represented by Formula 1, an ionic radius of X is greater than an ionic radius of oxygen.

15 . A lithium battery comprising:
a cathode; an anode; and an electrolyte disposed between the cathode and the anode, wherein the cathode, the anode, the electrolyte, or a combination thereof, comprises the solid-state electrolyte according to claim 1 .

16 . The lithium battery of claim 15 , wherein the lithium battery is a lithium ion battery, a solid-state battery, or a multilayer ceramic battery.

17 . A method of preparing a solid-state electrolyte comprising a compound represented by Formula 1, the method comprising:
providing a first material comprising a crystalline Li 5 AlO 4 and a lithium compound comprising a crystalline LiX, wherein X is Cl, Br, or a combination thereof; and mechanochemically contacting the first material and the lithium compound to prepare the amorphous compound represented by Formula 1
Li 5-4y Al 1-y X y O 4-4y-δ   Formula 1

wherein in Formula 1, 0.1≤y≤0.8 and 0≤δ<1, and X is Cl, Br, or a combination thereof, to prepare the solid-state electrolyte comprising the compound represented by Formula 1.

18 . The method of claim 17 , wherein the first material and the lithium compound are mixed in a molar ratio of about 9:1 to about 2:8.

19 . The method of claim 17 , wherein the mechanochemically contacting comprises mechanical milling to initiate a mechanochemical reaction, and the mechanical milling is carried out by a dry method in an inert atmosphere for about 10 hours to about 1,000 hours, and
the mechanochemical reaction is an exothermic reaction, and a temperature of the exothermic reaction is about 100° C. to about 500° C.

20 . The method of claim 17 , wherein the preparing of the solid-state electrolyte is carried out without additional heating.

Assignees

• Samsung Electronics Co Ltd

Inventors

• Kwon Giyun
• Ma Sangbok
• Gwon Hyeokjo
• Bae Youngjoon
• Yoon Gabin

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• C01F7/78

  Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements (aluminates C01F7/02; compounds containing aluminium, fluorine and alkali or alkaline earth metals C01F7/54; nitrates containing other cations besides aluminium C01F7/66; sulfides, sulfites or sulfates containing other cations besides aluminium C01F7/70 - C01F7/74) · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title