Solid electrolyte, preparation method thereof, metal air battery including the same, and electrochemical device including the same

Patent metadata

Field	Value
Publication number	US-11955597-B2
Application number	US-202016950206-A
Country	US
Kind code	B2
Filing date	Nov 17, 2020
Priority date	Dec 2, 2019
Publication date	Apr 9, 2024
Grant date	Apr 9, 2024

Abstract

A solid electrolyte including: an oxide represented by Formula 1, Formula 2, Formula 3, or a combination thereof,

Li 2+4x M1 1−x O 3   Formula 1

wherein, in Formula 1, M1 is hafnium, titanium, zirconium, or a combination thereof, and 0<x<1;

Li 2−y(a−4) M1 1−y M2 a y O 3   Formula 2

wherein, in Formula 2, M1 is hafnium, titanium, zirconium, or a combination thereof, M2 is at least one element having an oxidation number of a, and wherein a is an integer from 1 to 6, and 0<y<1; or

Li 2−z M1O 3−z X z   Formula 3

wherein, in Formula 3, M1 is hafnium, titanium, zirconium, or a combination thereof, X is a halogen, a pseudohalogen, or a combination thereof, and 0<z<2.

First claim

What is claimed is:

1. A solid electrolyte comprising:
an oxide represented by Formula 1, Formula 2, Formula 3, or a combination thereof,
Li 2+4x M1 1−x O 3   Formula 1

wherein, in Formula 1, M1 is hafnium, titanium, zirconium, or a combination thereof, and 0<x<1;
Li 2−y(a−4) M1 1−y M2 a y O 3   Formula 2

wherein, in Formula 2,
M1 is hafnium, titanium, zirconium, or a combination thereof,
M2 is at least one element having an oxidation number of a, and

wherein a is an integer from 1 to 6, and 0<y<1; or
Li 2−z M1O 3−z X z   Formula 3

wherein, in Formula 3,
M1 is hafnium, titanium, zirconium, or a combination thereof,
X is a halogen, a pseudohalogen, or a combination thereof, and 0<z<2.

2. The solid electrolyte of claim 1 , wherein, in Formulas 1 to 3, each M1 is independently hafnium, titanium, zirconium, or a combination thereof.

3. The solid electrolyte of claim 1 , wherein, in Formula 2, M2 is aluminum, gallium, indium, niobium, tantalum, vanadium, yttrium, lanthanum, scandium, magnesium, calcium, strontium, barium, zinc, cadmium, tungsten, molybdenum, a vacancy, or a combination thereof.

4. The solid electrolyte of claim 1 , wherein, in Formula 3, X is fluorine, chlorine, bromine, cyanide, cyanate, thiocyanate, azide, or a combination thereof.

5. The solid electrolyte of claim 1 , wherein, in Formula 1, x is about 0.01 to about 0.9.

6. The solid electrolyte of claim 1 , wherein, in Formula 2, y is about 0.05 to about 0.9.

7. The solid electrolyte of claim 1 , wherein, in Formula 2, a is 2, 3, 5, or 6.

8. The solid electrolyte of claim 1 , wherein, in Formula 3, z is about 0.05 to about 1.

9. The solid electrolyte of claim 1 , wherein the oxide of Formula 1 is an oxide represented by Formula 4, an oxide represented by Formula 5, or a combination thereof:
Li 2+4x Hf 1−x O 3   Formula 4

wherein, in Formula 4, 0.01≤x≤0.9, or
Li 2+4x Zr 1−x O 3   Formula 5

wherein, in Formula 5, 0.01≤x≤0.9.

10. The solid electrolyte of claim 1 , wherein the oxide of Formula 2 is an oxide represented by Formula 6, an oxide represented by Formula 7, or a combination thereof:
Li 2−y(a−4) Hf 1−y M2 a y O 3   Formula 6

wherein, in Formula 6,
M2 is aluminum, gallium, indium, niobium, tantalum, vanadium, yttrium, lanthanum, scandium, magnesium, calcium, strontium, barium, zinc, cadmium, tungsten, molybdenum, or a combination thereof,
a is an integer from 1 to 6, and 0.05≤y≤0.9, or
Li 2−y(a−4) Zr 1−y M2 a y O 3   Formula 7

wherein, in Formula 7,
M2 is aluminum, gallium, indium, niobium, tantalum, vanadium, yttrium, lanthanum, scandium, magnesium, calcium, strontium, barium, zinc, cadmium, tungsten, molybdenum, or a combination thereof,
a is an integer from 1 to 6, and 0.05≤y≤0.9.

11. The solid electrolyte of claim 1 , wherein the oxide of Formula 3 is an oxide represented by Formula 8, an oxide represented by Formula 9, or a combination thereof:
Li 2−z HfO 3−z X z   Formula 8

wherein, in Formula 8, X is a halogen, a pseudohalogen, or a combination thereof, and 0.05≤z≤1, or
Li 2−z ZrO 3−z X z

wherein, in Formula 9, X is a halogen, a pseudohalogen, or a combination thereof, and 0.05≤z≤1.

12. The solid electrolyte of claim 1 , wherein the oxide has a rock salt crystal structure.

13. The solid electrolyte of claim 1 , wherein the oxide has a C2/c space group.

14. The solid electrolyte of claim 1 , wherein the oxide is Li 2.2 Hf 0.95 O 3 , Li 1.9 HfF 0.1 O 2.9 , Li 1.8 HfF 0.2 O 2.8 , Li 1.5 HfF 0.5 O 2.5 , Li 1.9 HfCl 0.1 O 2.9 , Li 1.8 HfCl 0.2 O 2.8 , Li 1.5 HfCl 0.5 O 2.5 , Li 1.9 HfF 0.05 Cl 0.05 O 2.9 , Li 1.8 HfF 0.1 Cl 0.2 O 2.8 , Li 1.8 HfBr 0.1 Cl 0.1 O 2.8 , Li 1.5 HfF 0.25 Cl 0.25 O 2.5 , Li 1.5 HfBr 0.25 Cl 0.25 O 2.5 , Li 2.2 Hf 0.8 Y 0.2 O 3 , Li 2.2 Hf 0.8 La 0.2 O 3 , Li 2.2 Hf 0.8 Sc 0.2 O 3 , Li 2.2 Hf 0.8 Al 0.2 O 3 , Li 1.8 Hf 0.8 Ta 0.2 O 3 , Li 1.8 Hf 0.8 Nb 0.2 O 3 , Li 1.8 Hf 0.8 V 0.2 O 3 , Li 2.2 Hf 0.9 Mg 0.1 O 3 , Li 2.2 Hf 0.9 Ca 0.1 O 3 , Li 2.2 Hf 0.9 Sr 0.1 O 3 , Li 2.2 Hf 0.9 Ba 0.1 O 3 , Li 2.2 Hf 0.9 Zn 0.1 O 3 , Li 2.2 Hf 0.9 Cd 0.1 O 3 , Li 2.2 Zr 0.95 O 3 , Li 1.9 ZrF 0.1 O 2.9 , Li 1.8 ZrF 0.2 O 2.8 , Li 1.5 ZrF 0.5 O 2.5 , Li 1.9 ZrCl 0.1 O 2.9 , Li 1.8 ZrCl 0.2 O 2.8 , Li 1.5 ZrCl 0.5 O 2.5 , Li 1.9 ZrF 0.05 Cl 0.05 O 2.9 , Li 1.9 ZrBr 0.05 Cl 0.05 O 2.9 , Li 1.8 ZrF 0.1 Cl 0.1 O 2.8 , Li 1.8 ZrBr 0.1 Cl 0.1 O 2.8 , Li 1.5 ZrF 0.25 Cl 0.25 O 2.5 , Li 1.5 ZrBr 0.25 Cl 0.25 O 2.5 , Li 2.2 Zr 0.8 Y 0.2 O 3 , Li 2.2 Zr 0.8 La 0.2 O 3 , Li 2.2 Zr 0.8 Sc 0.2 O 3 , Li 2.2 Zr 0.8 Al 0.2 O 3 , Li 1.8 Zr 0.8 Ta 0.2 O 3 , Li 1.8 Zr 0.8 Nb 0.2 O 3 , Li 1.8 Zr 0.8 V 0.2 O 3 , Li 2.2 Zr 0.9 Mg 0.1 O 3 , Li 2.2 Zr 0.9 Ca 0.1 O 3 , Li 2.2 Zr 0.9 Sr 0.1 O 3 , Li 2.2 Zr 0.9 Ba 0.1 O 3 , Li 2.2 Zr 0.9 Zn 0.1 O 3 , Li 2.2 Zr 0.9 Cd 0.1 O 3 , Li 2.2 Hf 0.8 Ta 0.2 O 3 , Li 2.2 Hf 0.8 Nb 0.2 O 3 , Li 2.2 Hf 0.8 V 0.2 O 3 , Li 2.2 Zr 0.8 Ta 0.2 O 3 , Li 2.2 Zr 0.8 Nb 0.2 O 3 , Li 2.2 Zr 0.8 V 0.2 O 3 , or a combination thereof.

15. The solid electrolyte of claim 1 , wherein the solid electrolyte has an ion conductivity of about 1×10 −10 Siemens per centimeter or more at 25° C.

16. The solid electrolyte of claim 1 , wherein the oxide has a diffraction peak from a (02 1 ) crystal plane, a (11 2 ) crystal plane, and a (22 1 ) crystal plane, when analyzed by X-ray diffraction using Cu Kα radiation.

17. The solid electrolyte of claim 1 , wherein, a diffraction peak is present at a diffraction angle of about 26.7±0.5 °2θ, about 35±0.5 °2θ, about 39±0.5 °2θ, or a combination thereof, when analyzed by X-ray diffraction using Cu Kα radiation.

18. The solid electrolyte of claim 1 , wherein the solid electrolyte has a pellet density of about 2.6 grams per cubic centimeter to about 5.1 grams per cubic centimeter.

19. A metal air battery comprising:
a cathode;
an anode; and
an electrolyte between the cathode and the anode,
wherein the cathode, the anode, the electrolyte, or a combination thereof, comprises the solid electrolyte of claim 1 .

20. The metal air battery of 19 , wherein the anode comprises lithium and the cathode is configured to use air as an active material.

21. An electrochemical device comprising:
the solid electrolyte of claim 1 .

22. The electrochemical device of claim 21 , wherein the electrochemical devices comprises an anode; a cathode; and the solid electrolyte is between the anode and the cathode.

23. The electrochemical device of claim 21 , wherein the electrochemical device is a battery, an accumulator, a supercapacitor, a fuel cell, a sensor, or an electrochromic device.

24. A method of preparing a solid electrolyte, the method comprising:
mixing a lithium precursor, and an M1 precursor, to prepare a precursor mixture; and
heat-treating the precursor mixture to prepare the solid electrolyte of claim 1 , and an M2 precursor, and an X precursor are optionally added to the precursor mixture.

25. The method of claim 24 , wherein heat-treating of the precursor mixture comprises heat-treating at about 400° C. to about 950° C.

26. The method of claim 24 , further comprising pulverizing the heat-treated precursor mixture to form a pulverized product; and
heat-treating the pulverized product.

27. The method of claim 26 , wherein heat-treating of the pulverized product comprises heat-treating at about 500° C. to about 1300° C.

Assignees

• Samsung Electronics Co Ltd

Inventors

• Ma Sangbok
• Seo Donghwa

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title

• H01M12/06

  with one metallic and one gaseous electrode · CPC title

• H01M12/08

  composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type · CPC title

• H01M50/431

  Inorganic material · CPC title